Complexes Of Imidazole Ligands

ABSTRACT

Metal imidazolate complexes are described where imidazoles ligands functionalized with bulky groups and their anionic counterpart, i.e., imidazolates are described. Compounds comprising one or more such polyalkylated imidazolate anions coordinated to a metal or more than one metal, selected from the group consisting of alkali metals, transition metals, lanthanide metals, actinide metals, main group metals, including the chalcogenides, are contemplated. Alternatively, multiple different imidazole anions, in addition to other different anions, can be coordinated to metals to make new complexes. The synthesis of novel compounds and their use to form thin metal containing films is also contemplated.

CROSS REFERENCE TO RELATED APPLICATION

The present patent application is a division of U.S. patent applicationSer. No. 13/152,885 filed Jun. 3, 2011 and claims the benefit of priorU.S. Provisional Patent Application Ser. No. 61/354,023 filed Jun. 11,2010.

BACKGROUND OF THE INVENTION

The semiconductor fabrication industry continues to source volatilemetal containing precursors for vapor deposition processes, includingchemical vapor deposition (CVD) and atomic layer deposition (ALD),plasma-enhanced ALD (PEALD) pulsed CVD, plasma enhanced CVD (PECVD) forfabricating conformal metal containing films on substrates, such as:silicon, metal, metal nitride, metal silicon nitride, metal oxide andother metal-containing layers, using these metal-containing precursors.The range of metals include those of the main group elements, transitionmetals, lanthanides and actinides. There is also a growing interest involatile sources of chalcogenide based films containing such elements asgermanium, antimony and tellurium for the growth of Phase ChangeMaterials (PCM) for advanced memory applications. Additionally, any ofthese films can also be grown by super critical fluid deposition wherethe precursor is dissolved in a super critical fluid and a thin filmgrown from it.

For a metal compound to be useful as a volatile source for growing ametal containing film using the above mentioned processes it istypically important that it is stable enough to readily evaporate atelevated temperatures without decomposing, and similarly that its vaporis also themally stable. This is acutely important for depositionprocesses such as ALD where the precursor vapor must be able to endurevery high temperatures with no thermal decomposition occurring so thatthe film growth only occurs when the ALD reagent is cyclically addedduring the processing to build the growing film one layer at a time. Ifthermal decomposition of the precursor occurs then this effectively addsan undesired CVD component to the process and the step coverage of thegrowing film is degraded. In this respect, thermal stability of aprecursor is highly prized. However, many precursors fall short of thisideal situation by decomposing at elevated temperatures. Currently, amajor use of ALD in the semiconductor industry is the growth of metaloxides such as titanium oxide, zirconium oxide and lanthanide oxides.Often these processes are required to grow perfectly conformal filmsinto deeply bored cyclindrical volumes (vias) where it is imperativethat there is no thermal decomposition or CVD component that willdegrade conformality. One major mechanism by which precursors thermallydegrade is when the anionic ligand to which the metal coordinates startsto decompose. Thus, making metal precursors which are coordinated toanions which are thermally robust is highly desirable.

Prior art in this field includes; WO 20099/086263 A1; US20090209777;US20090202740; US 2009/0200524; Journal of the American ChemicalSociety, 131, 4022-4026, 2009; M. Tadokoro, T. Shiomi, K. Isob, K.Nakasuji, Inorganic Chem. 40 5476-5478 (2001); Inorg. Chem. 2008, 47,2196-2204; applicant's own pending patent applications U.S. Ser. No.12/785,041 priority May 29, 2009 and U.S. Ser. No. 61/301,824 filed Feb.5, 2010.

The prior art has attempted to provide precursors for theseapplications. However, none of the metal complexes in the prior artshare the special characteristic of the complexes disclosed in thepresent invention. The compounds disclosed herein are exceptional intheir volatility and thermal stability under conditions of vaporization.This makes them highly effective as precursors for thin film growth andany other application which requires volatile sources of metal,metalloids or chalcogenides.

BRIEF SUMMARY OF THE INVENTION

The present invention provides new metal complexes utilizing stericallyhindered imidazolate ligands where at least one of carbons of theimidazolate are substituted with C₁-C₁₀ primary, secondary or tertiaryalkyl; C₁-C₁₀ primary, secondary or tertiary alkoxy; C₁-C₁₀ primary,secondary or tertiary alkylamine; C₁-C₁₀ primary, secondary or tertiaryalkyl functionalized with a heteroatom substituted ring structureselected from the group consisting of imidazole, pyrrole, pyridine,furan, pyrimidine, pyrazole; C₁-C₁₀ alkyl functionalized with an amidegroup; C₁-C₁₀ primary, secondary or tertiary alkyl functionalized withan ester group and mixtures thereof. These ring substituted groups aresufficiently bulky to induce ‘eta-5’ bonding of the imidazolate withmetals, or eta-4, or eta-3 or eta-2 or eta-1 bonding to the metal. Inaddition, the bulk of the groups substituted on the imidazole anion isalso carefully selected to be complementary to the bulk of othersubstituted imidazolates present and/or the bulk of othernon-imidazolate anions and neutral ligands present so as to provide acoordinating environment to the metal which permits the formation ofvolatile monomeric or dimeric complexes, rather than involatilepolymeric complexes.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 shows the structure of 2,4-di-tert-butylimidazole, as determinedby X-ray crystallography.

FIG. 2 is shows the structure of 2,4,5-tri-tert-butylimidazole, asdetermined by X-ray crystallography.

FIG. 3 shows the structure of di-titaniumbis(2,4-di-tert-butylimidazolate)hexa(ethoxide), as determined by X-raycrystallography.

FIG. 4 shows the thermogravimetric analysis/differential scanningcalorimetry (TGA/DSC) for di-titaniumbis(2,4-di-tert-butylimidazolate)hexa-ethoxide.

FIG. 5 shows di-titaniumbis(2,4-di-tert-butylimidazolate)hexa-isopropoxide, as determined byX-ray crystallography.

FIG. 6 shows the TGA/DSC for di-titaniumbis(2,4-di-tert-butylimidazolate) hexa-isopropoxide.

FIG. 7 shows titaniumbis(2,4-di-tert-butylimidazolate)bis(isopropoxide), as determined byX-ray crystallography.

FIG. 8 shows titanium (2,4,5-tri-tert-butylimidazolate)tri-isopropoxide,as determined by X-ray crystallography.

FIG. 9 shows the TGA/DSC for titanium(2,4,5-tri-tert-butylimidazolate)tri-isopropoxide.

FIG. 10 shows titanium (2,4,5-tri-tert-butylimidazolate)trichloride, asdetermined by X-ray crystallography.

FIG. 11 shows titanium(2-tert-butyl-4,5-(1,1-dimethylpropyl)imidazolate)trichloride, asdetermined by X-ray crystallography.

FIG. 12 shows the TGA/DSC for cobalt(2,4,5-tri-tert-butylimidazolate)(cyclopentadienide).

FIG. 13 shows the TGA/DSC for cobalt(2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazolate)(cyclopentadienide).

FIG. 14 shows iron(2,4,5-tri-tert-butyl-imidazolate)(cyclopentadienide), as determined byX-ray crystallography.

FIG. 15 shows the TGA/DSC for iron(2,4,5-tri-tert-butylimidazolate)(cyclopentadienide).

FIG. 16 shows ruthenium(2,4,5-tri-methylimidazolate)(pentamethylcyclopentadienide), asdetermined by X-ray crystallography.

FIG. 17 shows the TGA/DSC for ruthenium(2,4,5-tri-methylimidazolate)(pentamethylcyclopentadienide).

FIG. 18 shows the TGA/DSC for ruthenium(2-ethyl-4-methylimidazolate)(pentamethylcyclopentadienide).

FIG. 19 shows ruthenium(2-tert-butyl-4-methyl-5-ethylimidazolate)(pentamethylcyclopentadienide),as determined by X-ray crystallography.

FIG. 20 shows the TGA/DSC for ruthenium(2-tert-butyl-4-methyl-5-ethylimidazolate)(pentamethylcyclopentadienide).

FIG. 21 shows ruthenium(2-tert-butyl-4,5-di-(1,1-dimethyl)imidazolate)(pentamethylcyclopentadienide),as determined by X-ray crystallography.

FIG. 22 shows the TGA/DSC for manganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate tricarbonyl.

FIG. 23 shows DSC for manganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate tricarbonyl (solidline) superimposed with the DSC for manganese(methylcyclopentadienide)tricarbonyl (dashed line).

FIG. 24 showslanthanum(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)di-iodidebis(tetrahydrofuran), as determined by X-ray crystallography.

FIG. 25 showscerium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)di-iodidebis(tetrahydrofuran), as determined by X-ray crystallography.

FIG. 26 shows europium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate) iodidebis(tetrahydrofuran), as determined by X-ray crystallography.

FIG. 27 shows di-europium tetra(2,4,5-tri-tert-butylimidazolate), asdetermined by X-ray crystallography.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new monomeric or dimeric Group 3 to Group16 metal complexes comprising sterically hindered mono-negativeimidazolate, derived by deprotonation of imidazole ligands, representedby the formula below

R¹⁻³ can be selected from hydrogen, linear or cyclic or branched C₁₋₁₀alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl, aromatic, and optionallyfurther derivatized with other functional groups, such as; amine,hydroxyl, carboxylic, substituted amine and similar derivatives, whereinat least one of R¹, R² or R³ is not hydrogen; preferably at least R¹ andR² are not hydrogen, and most preferably R¹, R² and R³ are not hydrogen.

For the purpose of this invention sterically hindered mono-negativeimidazolate ligands are selected to prevent formation of metalcoordination polymers and to provide new monomeric or dimericimidazolate metal complexes. For the purpose of this invention monomericand dimeric complexes are metal complexes which readily form monomersand dimers at sufficiently low temperature <300° C. While it is wellunderstood that higher order of coordination can be present whencompounds of this invention are solids, steric hinderence aroundimidazolate ligands prevents strong intermolecular interactions betweenindividual molecules. Thus, imidazolate complexes of this inventionexists in monomeric or dimeric form already below 300° C., which allowsthese complexes to be sufficiently volatile with vapor pressure >0.01torr at 200° C., preferably >0.1 torr at 200° C., and have low meltingpoint <300° C., preferably <200° C., and more preferably <100° C. Thesephysical properties are highly desirable for use of these materials forchemical vapor deposition of metal containing films.

The monomeric or dimeric metal imidazole complexes of this inventionalso evaporate cleanly by thermogravimetric analysis (TGA) withinvolatile residues <20 wt %, preferably <10 wt %, more preferably <5 wt%.

In contrast imidazolate complexes of the prior art do not have enoughsteric hinderence around the imidazolate ligands to prevent bridging ofmetal cations. Imidazolate complexes of the prior art tend to formstrong polymeric complexes, known in the art as zeolitic imidazolateframeworks, as for example illustrated in Formula A. These complexes ofthe prior art are highly associated, and as such are involatile.

However, the metal imidazolate complexes of this disclosure overcome theabove tendency towards polymerization by utilizing imidazole ligandswhich contain at least one substituent, preferably at the 2 position, tohelp disrupt coordination polymer formation, as above. As explained bythe examples of this invention, for some metal complexes, it isadvantageous to have bulky groups such as tert-butyl bonded to the 2, 4,and 5 carbon atoms of imidazole ring. For some ions, it is advantageousto have alkyl groups bonded to the 2, 4 and 5 carbon atoms that aresmaller. In these examples, the alkyl groups can enable improvedliquidity properties, while also providing lower molecular weight forimproved volatility. Alkyl groups such as, but not limited to: methyl,ethyl, vinyl, propyl, isopropyl can be incorporated into the 2, 4 and/or5 positions to optimize the properties for a given imidazolate anion toinduce it to coordinate to a metal ion in novel ways, such as eta-5 asshown below in Formula B, thereby avoiding coordination polymerformation.

Thus, bulky groups for the purpose of the present invention are groups,which have sufficient 3-dimensional spacial form to create enough sterichindrance to preclude the bonding illustrated in Formula A, so thatmetals bonding with the imidazolates of the present invention areenabled to be preferably bonded in the ‘eta-5’ bonding or end on eta-1bonding (no-coplanar bonding), as illustrated in Formulae B, C and D,respectively.

Other bonding modes between these two extremes are also possible, suchas eta-2, eta-3 and eta-4.

The structure depicted in Formula B represents an unexpected result, inthat the vast preponderance of imidazole anions (ie imidazolates) do notbind in an ‘eta-5’ or sideways manner, but rather ‘end on’ only throughboth the imidazolate's nitrogen atoms, as in Formula A. Direct evidenceof this eta-5 coordination is provided by single crystal X-ray analysisin Examples 22, 23, 29, 30, 32, 33, 38 and 39 herein. In the Cambridgecrystallographic data base, there is only one example of an eta-5metal-to-imidazolate ion coordination (M. Tadokoro, T. Shiomi, K. Isob,K. Nakasuji, Inorganic Chem. 40 5476-5478 (2001)), and it occurs in aninvolatile mixed metal polymeric coordination compound, rather than inthe discreet and volatile metal complexes of the present invention,further underscoring the unique character of the present invention'snovel imidazole ligands.

In addition to the novel ‘eta-5’ bonding described above, theimidazolate ligands of this disclosure can also bind in a novel ‘end on’mode where just one of the two nitrogens of the imidazolate bind to ametal center, as shown below in Formula C. Direct evidence of this eta-1coordination is provided by single crystal X-ray analysis in Examples16, 18, 19 and 20 herein. In the Cambridge data base, there is also onlyone example of an eta-1 binding imidazolate anion, but this occurs in abimetallic iron/sodium imidazolate/nitrate 18-crown-6 complex, notreported as volatile, in contrast to the volatile molecules containingimidazole based anions, as described in this disclosure.

In addition, when the steric requirements of the imidazole substituentsare met, as above, an additional unique bridging mode exists, where themetal-to-imidazolate anion bonds are non-coplanar with the plane of theimidazolate anion, but with both metal-to imidazolate bonds orientedtowards the same face of the imidazolate anion. In this way, a dimericstructure containing two metal ions can be prepared. Examples of thisare depicted, below, in Formula D.

To understand the unique character of the novel metal imidazolatecompounds of this disclosure, it is instructive to consider thestructure and substitutional numbering system of unsubstitutedimidazole, as shown in Formula E, and imidazolate anion shown in FormulaF. Note that the ring numbering system indicates that when all threecarbon atoms of the imidazole ring are substituted with alkyl groups,then the resulting molecule would be called a 2,4,5-trialkylimidazole.

When the N—H group of imidazole is deprotonated at position 1, theresulting formal negative charge of the anion thus created isdelocalized throughout the five membered ring. However, if such an anioncoordinates to metal cations, it will typically only do so through bothof the nitrogen atoms, not involving the three carbon atoms of the ring.In this way, the imidazole anion most typically behaves as a ‘bridginganion’ between metal centers.

Bulky groups can comprise C₃₋₁₂ groups, preferably branched alkyl,cyclic or aromatic, and optionally further derivatized with otherfunctional groups, such as; amine, hydroxyl, carboxylic, substitutedamine and similar derivatives. Alkanes, alkenes, alkynes, cyclic formsof the same, aromatics, and their derivatives are all contemplated asbulky groups, as long as they meet the requirement of having sufficientbulk in the form of 3-dimensional spacial form to induce ‘eta-5’ bondingof the imidazole with metals, or eta-4, or eta-3 or eta-2 or eta-1bonding to the metal. Other suitable bulky alkyl groups include, but notlimited to; methyl, ethyl, propyl, isopropyl, tert-amyl, neopentyl,adamantly, hexyl, cyclohexyl, propyl, butyl, isobutyl, tertbutyl,pentyl, isopentyl, neopenty, norbornyl, bicyclo[2.2.1]heptyl, amido,nitro; C₉-C₂₀ alkylphenyl, C₁-C₁₀ alkoxy; alkylamine; C₁-C₁₀ alkylfunctionalized with a heteroatom substituted ring structure selectedfrom the group consisting of imidazole, pyrrole, pyridine, furan,pyrimidine, pyrazole; C₁-C₁₀ alkyl functionalized with an amide group;C₁-C₁₀ alkyl functionalized with an ester group and mixtures thereof.

This invention discloses the complexation of sterically hinderedimidazolate anions to alkali metals, transition metals, lanthanidemetal, actinide metals, and main group elements, includingchalcogenides, to form new volatile molecules that can enjoy a widerange of utility, such as volatile precursors for thin film depositionby ALD/CVD.

The novel imidazolate based metal complexes of this disclosure aredemonstrated to be of high thermal stability. The alkyl substitutedimidazoles do not contain oxygen, which is a desirable property formetal-ligand systems, when used for metal and non-oxide dielectricdepositions. The lack of oxygen within the ligand system can preventoxidation, and the imidazoles should perform significantly better thantheir oxygen-containing counterparts in this regard. This inventiondiscloses metal imidazolate compounds, where the imidazolate anion doesnot coordinate to multiple metal centers to form compounds of highnuclearity or polymers, which are either of low volatility or areinvolatile. So, in summation, the anionic imidazolate ligands need tocoordinate a relatively low number of metal centers, such as 1 or 2; andare thermally very resilient against degradation.

To achieve such a highly stable anionic ligand also means that itsformal negative charge needs to be stabilized by the structure of theligand. The novel metal imidazolate compounds of this application arestabilized, due to the stability of the imidazolate anions upon whichthey are based. This stems from the ability of the imidazolate anions ofthis disclosure to stabilize their negative charge by being a fivemembered ring aromatic anion, which contains two nitrogen atoms. Theelectronegativity of the latter two atoms also increase the stability ofthe formal negative charge. Other five membered aromatic ring anionsexist, such as cyclopentadienyl, but these are not as stable as theimidazolate anions of this disclosure. Also important is the shape ofthe imidazolate anion, because if its structure bears large bulkygroups, such as tert-butyl, these can allow the nuclearity of theresulting metal complexes to be low, since bonding access to the ligandwill be limited to 1 or 2 metal centers. This allows the novelimidazolate compounds of this disclosure to be volatile and highlyuseful as precursors.

Besides these features, it is also important that the novel imidazolatemetal complexes of this disclosure include those that utilizeasymmetrically substituted imidazole ligands. This helps to lower thesymmetry of the imidazolate complex, which in turn can lower the crystallattice packing energies and lower the melting point of the metalcomplex. It is particularly important to make pure metal complexes oflowered melting point or a liquid, since liquid precursors are easier toevaporate than solid precursors, and low melting point solids tend to bemore soluble in solvents, to permit precursor delivery by DLI.

An example of the efficacy of this approach is found in the comparisonof the melting points ofruthenium(trimethylimidazolate)(pentamethylcyclopentadienide) andruthenium(2-ethyl-4-methylimidazolate)(pentamethylcyclopentadienide), aslisted in Examples 31 and 32, respectively. Whereas the symmetricaltrimethylimidazolate complex melts at 130.6° C., the asymmetric2-ethyl-4-methylimidazolate containing complex melts at 64.1° C.

Metal complexes of sterically hindered imidazole ligands are disclosed,along with the syntheses of the same, which are highly volatile andstable complexes, that are exceptionally useful as precursor moleculesfor CVD, ALD, and the like, thin film deposition processes.

Compounds are described comprised of one or more polyalkylatedimidazolate anions coordinated to a metal selected from the groupconsisting of a transition metal, a lanthanide metal, an actinide metalor main group element, including chalcogenides or mixtures thereof.

Alternatively, metal compounds can be made where a number of differentimidazolate anions may be coordinated to the metal. In otherembodiments, one or more imidazolate anions are coordinated to a metaland additional different anionic ligands are then also coordinated tothe metal to balance its positive charge. Thus, if the metal is M andits cationic charge is (n+), imidazole anion is (I) and (X), (Y) and (Z)are a non-imidazolate anions, then the new and novel metal compounds ofthis disclosure are expressed as:

(M^((n+)))_(z)(I)_(a)(X)_(b)(Y)_(c)(Z)_(d)(L)_(x)

where (n) can be 1-6, (z) can be one or two, (b), (c) and (d) canindividually range from zero to five, (a) can be from one to six withthe provision that a, b, c, d, n and z are selected to make metalcomplex electroneutral. When X, Y and Z are monoanions than(a)+(b)+(c)+(d)=(z)×(n). Additionally, when (a) is greater than unity,the imidazolate anions can be the same or different, i.e., two or moreunique imidazolate anions coordinate to the metal. L is a neutralcoordinating molecule, such as; an ether, polyether, furans, amine,polyamine or alkoxyamine, pyridine etc. (L) can also be an unsaturatedmolecule, such as; an olefin, diolefin, triolefin or polyolefin, alkyne,silylolefin, silyalkyne, which can form a stabilizing organometallicbond to the metal. Similarly, (L) can also be carbon monoxide, nitrile,isonitrile, silylnitrile or isocyanide, alkyl phosphine, aromaticphospine. Exemplary imidazoles from which the metal imidazolatecomplexes of this invention can be synthesized are as follows.

-   2-methylimidazole-   2-ethylimidazole-   2-propylimidazole-   2-isopropylimidazole-   2-tert-butylimidazole-   2-(1,1-dimethylpropyl)imidazole-   2,5-dimethylimidazole-   2-ethyl-4-methylimidazole-   2-propyl-4-methylimidazole-   2-isopropyl-4-methylimidazole-   2-tert-butyl-4-methylimidazole-   2-(1,1-dimethylpropyl)-4-methylimidazole-   2-methyl-4-ethylimidazole-   2,4-diethylimidazole-   2-propyl-4-ethylimidazole-   2-isopropyl-4-ethylimidazole-   2-tert-butyl-4-ethylimidazole-   2-(1,1-dimethylpropyl)-4-ethylimidazole-   2-methyl-4-propylimidazole-   2-ethyl-4-propylimidazole-   2,4-dipropylimidazole-   2-isopropyl-4-propylimidazole-   2-tert-butyl-4-propylimidazole-   2-(1,1-dimethylpropy)-4-propylimidazole-   2-methyl-4-isopropylimidazole-   2-ethyl-4-isopropylimidazole-   2-propyl-4-isopropylimidazole-   2,4-diisopropylimidazole-   2-tert-butyl-4-isopropylimidazole-   2-(1,1-dimethylpropyl)-4-isopropylimidazole-   2-methyl-4-tert-butylimidazole-   2-ethyl-tert-butylimidazole-   2-propyl-tert-butylimidazole-   2-isopropyl-4-tert-butylimidazole-   2,4-di-tert-butylimidazole-   2-(1,1-dimethylpropyl)-4-tert-butylimidazole-   2-methyl-4-(1,1-dimethylpropyl)imidazole-   2-ethyl-4-(1,1-dimethylpropyl)imidazole-   2-propyl-4-(1,1-dimethylpropyl)imidazole-   2-isopropyl-4-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2,4-di(1,1-dimethylpropyl)imidazole-   2,4,5-trimethylimidazole-   2-ethyl-4,5-dimethylimidazole-   2-propyl-4,5-dimethylimidazole-   2-isopropyl-4,5-dimethylmidazole-   2-tert-butyl-4,5-dimethylimidazole-   2-(1,1-dimethylpropyl)-4,5-dimethyl midazole-   2,4-dimethyl-5-ethylimidazole-   2,4-diethyl-5-methylimidazole-   2-propyl-4-methyl-5-ethylimidazole-   2-isopropyl-4-methyl-5-ethylimidazole-   2-tert-butyl-4-methyl-5-ethyl imidazole-   2-(1,1-dimethylpropyl)-4-methyl-5-ethylimidazole-   2,4-dimethyl-5-propylimidazole-   2-ethyl-4-methyl-5-propylimidazole-   2,4-dipropyl-5-methylimidazole-   2-isopropyl-4-methyl-5-propy imidazole-   2-tert-butyl-4-methyl-5-propylimidazole-   2-(1,1-dimethylpropyl)4-methyl-5-propylimidazole-   2-methyl-4-ethyl-5-propylimidazole-   2,4-diethyl-5-propylimidazole-   2,4-dipropyl-5-ethylimidazole-   2-isopropyl-4-ethyl-5-propyl imidazole-   2-tert-butyl-4-ethyl-5-propylimidazole-   2-(1,1-dimethylpropyl)-4-ethyl-5-propylimidazole-   2-methyl-4,5-diethylimidazole-   2,4,5-triethylethylimidazole-   2-propyl-4,5-diethylimidazole-   2-isopropyl-4,5-diethylimidazole-   2-tert-butyl-4,5-diethylimidazole-   2-(1,1-dimethylpropyl)-4,5-diethylimidazole-   2-methyl-4,5-dipropylimidazole-   2-ethyli-4,5-dipropylmidazole-   2,4,5-tripropylimidazole-   2-isopropyl-4,5-dipropylimidazole-   2-tert-buty-4,5-dipropylimidazole-   2-(1,1-dimethylpropyl)-4,5-dipropylimidazole-   2,4,5-tri-tert-butylimidazole-   2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4,5-di-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4,5-di-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-tert-butlyimidazole-   2,4,5-tri-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpropyl)-   2,4,5-tri-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4,5-di-(1,1-dimethylpropyl)limidazole-   2-(1,1-dimethylpentyl)-4,5-di-(1,1-dimethylbutyl)limidazole-   2,4,5-tri-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di-(1,1-dimethylhexyl)limidazole-   2-(1,1-dimethylhexyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4,5-di-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2,4,5-tri-(1,1-dimethylhexyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylbutyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylpentyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-tert-butyl-imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-tert-butyl-imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-tert-butyl-imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-tert-butyl-imidazole-   2,4-di-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylbutyl)-5-tert-butyl-imidazole-   2,4-di(1,1-dimethylbutyl)-5-tert-butyl-imidazole-   2,5-di(1,1-dimethylbutyl)-4-tert-butyl-imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-tert-butyl imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-tert-butylimidazole-   2,4-di(1,1-dimethylbutyl)-5-(1,1-dimethylpropylmidazole-   2,5-di(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-(1,1-dimethylbutyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-(1,1-dimethylbutyl)-4-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpentyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-di-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethyl butyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl butyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethyl hexyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl hexyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethyl    butyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl    butyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-di(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethyl    butyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl    butyl)-5-(1,1-dimethylpentyl)imidazole-   2,4-di(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)imidazole-   2-(1-methylethyl)-4,5-di-tert-butylimidazole-   2-(1-methylethyl)-4,5-di(1,1-dimethylpropyl)imidazole-   2-(1-methylethyl)-4,5-di(1,1-dimethylbutyl)imidazole-   2-(1-methylethyl)-4,5-di(1,1-dimethylpentyl)imidazole-   2-(1-methylethyl)-4,5-di(1,1-dimethylhexyl)imidazole-   2,4,5-tri(1-methylethyl)imidazole-   2-(1-methylethyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-tert-butylimidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-tert-butylimidazole-   2-(1-methylethyl)-4-tert-butylimidazole-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-tert-butylimidazole-   2-(1-methylethyl)-4-tert-butylimidazole-5-(1,1-dimethylpentyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-tert-butylimidazole-   2-(1-methylethyl)-4-tert-butylimidazole-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-tert-butylimidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)-imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)-imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)-imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)-imidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)-imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)-imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)-imidazole-   2,4-di-tert-butyl-5-(1-methylethyl)imidazole-   2,5-di-tert-butyl-4-(1-methylethyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-tert-butyl-4-(1-methylethyl)-5-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1-methylethyl)imidazole-   2-tert-butyl-4-(1-methylethyl)-5-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1-methylethyl)imidazole-   2-tert-butyl-4-(1-methylethyl)-5-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1-methylethyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1-methylethyl)-5-tert-butylimidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1-methylethyl)imidazole-   2,4-di(1,1-dimethylpropyl)-5-(1-methylethyl)-imidazole-   2,5-di(1,1-dimethylpropyl)-4-(1-methylethyl)-imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1-methylethyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-tert-butyl-5-imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylbutyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpenyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylethyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylethyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylpropyl)-5-midazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylbutyl)-5-midazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylethyl)imidazole-   2,4-di(1,1-dimethylpentyl)-5-(1,1-dimethylethyl)imidazole-   2,5-di(1,1-dimethylpentyl)-4-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylhexyl)-5-midazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylethyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylethyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylbutyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1-methylethyl)-5-(1,1-dimethylbutyl)-5    imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1-methylethyl)-5-(1,1-dimethylpentyl)    imidazole-   2,4-di(1,1-dimethylhexyl)-5-(1-methylethyl)imidazole-   2,5-di(1,1-dimethylhexyl)-4-(1-methylethyl)imidazole-   2,4-(1-methylethyl)-5-tert-butylimidazole-   2,5-(1-methylethyl)-4-tert-butylimidazole-   2,4-(1-methylethyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-(1-methylethyl)-4-(1,1-dimethylpropyl)imidazole-   2,4-(1-methylethyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-(1-methylethyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-(1-methylethyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-(1-methylethyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-(1-methylethyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-(1-methylethyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1,2-dimethylpropyl)-4,5-di-tert-butylimidazole-   2-(1,2-dimethylpropyl)-4,5-di-(1,1-dimethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4,5-di-(1,1-dimethylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2-(1,2-dimethylpropyl)-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,2-dimethylpropyl)-4,5-di-(1-methylethyl)imidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethypropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethypropyl)-5-tert-butylimidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-tert-butylimidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethypentyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethypentyl)-5-tert-butylimidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethyhexyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethyhexyl)-5-tert-butylimidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-(1,1-dim    ethypentyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dim    ethypentyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethyhexyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethyhexyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dim    ethypentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethypentyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethyhexyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethyhexyl)imidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1-methyethyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methyethyl)-5-tert-butylimidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1-methyethyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methyethyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-(1-methyethyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methyethyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-(1-methyethyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methyethyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methyethyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methyethyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methyethyl)imidazole-   2,4-di-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2,5-di-tert-butyl-4-(1,2-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-tert-butylimidazole-   2,4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,2-dimethylpropyl)-5-imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2,4-di(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-di(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)-5-imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)-5-imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1-methylethyl)-5-imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5(-1,2-dimethylpropyl)-5imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,4-di(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl))imidazole-   2,5-di(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl))imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2,4-di(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-di(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-tert-butyl-imidazole-   2-(1-methylethyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2,4-di(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-di(1-methylethyl)-4-(1,2-dimethylpropyl)imidazole-   2,4-di(1,2-dimethylpropyl)-5-tert-butylimidazole-   2,5-di(1,2-dimethylpropyl)-4-tert-butylimidazole-   2,4-di(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)imidazole-   2,4-di(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1,2-dimethylpropyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di(1,2-dimethylpropyl)-4-(1,1-dimethylhexyl)imidazole-   2,4-di(1,2-dimethylpropyl)-5-(1-methylethyl)imidazole-   2,5-di(1,2-dimethylpropyl)-4-(1-methylethyl)imidazole-   Preferably the imidazole is-   2,4,5-tri-tert-butylimidazole-   2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4,5-di-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4,5-di-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-tert-butlyimidazole-   2,4,5-tri-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpropyl)-   2,4,5-tri-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4,5-di-(1,1-dimethylpropyl)limidazole-   2-(1,1-dimethylpentyl)-4,5-di-(1,1-dimethylbutyl)limidazole-   2,4,5-tri-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di-(1,1-dimethylhexyl)limidazole-   2-(1,1-dimethylhexyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4,5-di-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di-(1,1-dimethylpentyl)imidazole-   2,4,5-tri-(1,1-dimethylhexyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylbutyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylpentyl)imidazole-   2,4-di-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2,5-di-tert-butyl-4-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-tert-butyl-imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-tert-butyl-imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-tert-butyl-imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-tert-butyl-imidazole-   2,4-di-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylbutyl)-5-tert-butyl-imidazole-   2,4-di(1,1-dimethylbutyl)-5-tert-butyl-imidazole-   2,5-di(1,1-dimethylbutyl)-4-tert-butyl-imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-tert-butyl imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-tert-butylimidazole-   2,4-di(1,1-dimethylbutyl)-5-(1,1-dimethylpropylmidazole-   2,5-di(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-(1,1-dimethylbutyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-(1,1-dimethylbutyl)-4-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpentyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-tert-butylimidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-di-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethyl butyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl butyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1,1-dimethyl hexyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl hexyl)-5-tert-butylimidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethyl    butyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl    butyl)-5-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)imidazole-   2,4-di(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1,1-dimethyl    butyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethyl    butyl)-5-(1,1-dimethylpentyl)imidazole-   2,4-di(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)imidazole

Preferably the imidazole is

-   2,4,5-tri-tert-butylimidazole-   2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di-tert-butylimidazole-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpropyl)imidazole-   2-tertbutyl-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2,4,5-tri(1-methyl-1-ethylpropyl)imidazole-   2,4-di-ter-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-di-ter-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1-methylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1-methylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,2-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-di(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-di(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-4-di(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-5-di(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-di(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-di(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-5-(1,2-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-(1,2-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(dimethylpentyl)-4-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(dimethylpentyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methylethyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(1-methylethyl)-4-(1,2-dimethylpropyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-tert-butylimidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-tert-butylimidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylhexyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1-methylethyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1-methylethyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,2-dimethylpropyl)imidazole-   2-tertbutyl-4,5-di(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methylpropyl)imidazole-   2-(1-methylethyl)-4,5-di(1-methylpropyl)imidazole-   2,4,5-tri(1-methylpropyl)imidazole-   2,4-di-ter-butyl-5-(1-methylpropyl)imidazole-   2,5-di-ter-butyl-4-(1-methylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2-tert-butyl-4-(1-methylpropyl)-5-(1-methylpropyl)imidazole-   2-tert-butyl-5-(1-methylpropyl)-4-(1-methylpropyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-tert-butyl-5-(1,2-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-tert-butyl-4-(1-methylpropyl)imidazole-   2,4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1-methylethyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1-methylethyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-tert-butyl-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2,4-di(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2,5-di(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1-methylethyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-tert-butyl-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-4-di(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-5-di(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1-methylethyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1-methylethyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-tert-butyl-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2,4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2,5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1-methylethyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1-methylethyl)-4-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1-methylethyl)-4-tert-butyl-5-(1-methylpropyl)imidazole-   2-(1-methylethyl)-5-tert-butyl-4-(1-methylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2,4-di(1-methylethyl)-5-(1-methylpropyl)imidazole-   2,5-di(1-methylethyl)-4-(1-methylpropyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1-methylethyl)-5-(1,2-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-tert-butyl-4-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methylethyl)-5-(1-methylpropyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1-methylethyl)-4-(1-methylpropyl)imidazole-   2,4-(1,2-dimethylpropyl)-5-(1-methylpropyl)imidazole-   2,5-(1,2-dimethylpropyl)-4-(1-methylpropyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylpropyl)-5-tert-butyl-4-(1,1-dimethylbutyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1-methylpropyl)-5-tert-butyl-4-(1,1-dimethylpentyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylpropyl)-5-tert-butyl-4-(1,1-dimethylhexyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methylpropyl)-4-(dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylpropyl)-5-(dimethylpentyl)-4-(1,1-dimethylbutyl)imidazole-   2-(1-methylpropyl)-4-(dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylpropyl)-5-(dimethylpentyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1-methylethyl)imidazole-   2-(1-methylpropyl)-5-tert-butyl-4-(1-methylethyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methylethyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methylethyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methylethyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methylethyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methylethyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methylethyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methylethyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-tert-butyl-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylpropyl)-5-(1-methylethyl)-4-(1,2-dimethylpropyl)imidazole-   2,4-di(1-methylpropyl)-5-tert-butylimidazole-   2,5-di(1-methylpropyl)-4-tert-butylimidazole-   2,4-di(1-methylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1-methylpropyl)-4-(1,1-dimethylpropyl)imidazole-   2,4-di(1-methylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di(1-methylpropyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di(1-methylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1-methylpropyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di(1-methylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di(1-methylpropyl)-4-(1,1-dimethylhexyl)imidazole-   2,4-di(1-methylpropyl)-5-(1-methylethyl)imidazole-   2,5-di(1-methylpropyl)-4-(1-methylethyl)imidazole-   2,4-di(1-methylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-di(1-methylpropyl)-4-(1,2-dimethylpropyl)imidazole-   2-tertbutyl-4,5-di(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methylbutyl)imidazole-   2-(1-methylethyl)-4,5-di(1-methylbutyl)imidazole-   2,4,5-tri(1-methylbutyl)imidazole-   2,4-di-ter-butyl-5-(1-methylbutyl)imidazole-   2,5-di-ter-butyl-4-(1-methylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2-tert-butyl-5-(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2-tert-butyl-5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2-tert-butyl-4-(1-methylbutyl)-5-(1-methylbutyl)imidazole-   2-tert-butyl-5-(1-methylbutyl)-4-(1-methylbutyl)imidazole-   2-tert-butyl-4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-tert-butyl-5-(1,2-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-5-tert-butyl-4-(1-methylbutyl)imidazole-   2,4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1-methylethyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1-methylethyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-5-tert-butyl-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2,4-di(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2,5-di(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1-methylethyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1-methylethyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-5-tert-butyl-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-4-di(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-5-di(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1-methylethyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1-methylethyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-5-tert-butyl-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2,4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2,5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1-methylethyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1-methylethyl)-4-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1-methylethyl)-4-tert-butyl-5-(1-methylbutyl)imidazole-   2-(1-methylethyl)-5-tert-butyl-4-(1-methylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2-(1-methylethyl)-4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2-(1-methylethyl)-5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2,4-di(1-methylethyl)-5-(1-methylbutyl)imidazole-   2,5-di(1-methylethyl)-4-(1-methylbutyl)imidazole-   2-(1-methylethyl)-4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1-methylethyl)-5-(1,2-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-tert-butyl-5-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-5-tert-butyl-4-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-4-(1-methylethyl)-5-(1-methylbutyl)imidazole-   2-(1,2-dimethylpropyl)-5-(1-methylethyl)-4-(1-methylbutyl)imidazole-   2,4-(1,2-dimethylpropyl)-5-(1-methylbutyl)imidazole-   2,5-(1,2-dimethylpropyl)-4-(1-methylbutyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylbutyl)-5-tert-butyl-4-(1,1-dimethylbutyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1-methylbutyl)-5-tert-butyl-4-(1,1-dimethylpentyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylbutyl)-5-tert-butyl-4-(1,1-dimethylhexyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methylbutyl)-4-(dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1-methylbutyl)-5-(dimethylpentyl)-4-(1,1-dimethylbutyl)imidazole-   2-(1-methylbutyl)-4-(dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1-methylbutyl)-5-(dimethylpentyl)-4-(1,1-dimethylhexyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1-methylethyl)imidazole-   2-(1-methylbutyl)-5-tert-butyl-4-(1-methylethyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(1-methylethyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylpropyl)-4-(1-methylethyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylbutyl)-5-(1-methylethyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylbutyl)-4-(1-methylethyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpentyl)-5-(1-methylethyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylpentyl)-4-(1-methylethyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylhexyl)-5-(1-methylethyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylhexyl)-4-(1-methylethyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-tert-butyl-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-tert-butyl-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpropyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylbutyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylpentyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylpentyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-(1,1-dimethylhexyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-(1,1-dimethylhexyl)-4-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-4-(1-methylethyl)-5-(1,2-dimethylpropyl)imidazole-   2-(1-methylbutyl)-5-(1-methylethyl)-4-(1,2-dimethylpropyl)imidazole-   2,4-di(1-methylbutyl)-5-tert-butylimidazole-   2,5-di(1-methylbutyl)-4-tert-butylimidazole-   2,4-di(1-methylbutyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1-methylbutyl)-4-(1,1-dimethylpropyl)imidazole-   2,4-di(1-methylbutyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di(1-methylbutyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di(1-methylbutyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1-methylbutyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di(1-methylbutyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di(1-methylbutyl)-4-(1,1-dimethylhexyl)imidazole-   2,4-di(1-methylbutyl)-5-(1-methylethyl)imidazole-   2,5-di(1-methylbutyl)-4-(1-methylethyl)imidazole-   2,4-di(1-methylbutyl)-5-(1,2-dimethylpropyl)imidazole-   2,5-di(1-methylbutyl)-4-(1,2-dimethylpropyl)imidazole

More preferably, the imidazole is one of:

-   2-tertbutyl-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2-(1-methylethyl)-4,5-di(1-methyl-1-ethylpropyl)imidazole-   2,4,5-tri(1-methyl-1-ethylpropyl)imidazole-   2,4-di-ter-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-di-ter-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-tert-butyl-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1-methylethyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1-methylethyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-4-(1,2-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpropyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-di(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-di(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylbutyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-4-di(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-5-di(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylpentyl)-5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-tert-butyl-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-tert-butyl-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpropyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpropyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylbutyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylbutyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-4-(1,1-dimethylpentyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2-(1,1-dimethylhexyl)-5-(1,1-dimethylpentyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2,4-(1,1-dimethylhexyl)-5-(1-methyl-1-ethylpropyl)imidazole-   2,5-(1,1-dimethylhexyl)-4-(1-methyl-1-ethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylpropyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-tert-butyl-5-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-tert-butyl-4-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylpentyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)-5-(dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(dimethylpentyl)-5-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(dimethylpentyl)-4-(1,1-dimethylbutyl)imidazole-   2-(1-methyl-1-ethylpropyl)-4-(dimethylpentyl)-5-(1,1-dimethylhexyl)imidazole-   2-(1-methyl-1-ethylpropyl)-5-(dimethylpentyl)-4-(1,1-dimethylhexyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-tert-butylimidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-tert-butylimidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpropyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpropyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylbutyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylbutyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylpentyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylpentyl)imidazole-   2,4-di(1-methyl-1-ethylpropyl)-5-(1,1-dimethylhexyl)imidazole-   2,5-di(1-methyl-1-ethylpropyl)-4-(1,1-dimethylhexyl)imidazole

Preferably, the imidazole is 2-tert-butyl-4,5-di-tert-amylimidazole.

Preferably, the imidazole is 2-tert-amyl-4,5-di-tert-butylimidazole.

Preferably, the imidazole is2-tert-butyl-4-tert-amyl-5-tert-butylimidazole.

Preferably, the imidazole is2-tert-amyl-4-tert-butyl-5-tert-amylimidazole.

Preferably, the imidazole is 2,4,5-trimethylimidazole.

Preferably, the imidazole is 2-tert-butyl-4-methyl-5-ethylimidazole.

Preferably, the imidazole is 2-ethyl-4-methylimidazole.

Preferably, the imidazole is2-isopropyl-4,5-di(1,1-dimethylpropyl)imidazole.

Preferably, the imidazole is 2-sec-butyl-4,5-di-tert-butylimidazole.

Preferably, the imidazole is2-(1-ethyl-propyl)-4,5-di-isopropylimidazole.

Preferably, the imidazole is 2-tert-butyl-4,5-di-isopropylimidazole.

For the purpose of this invention methyl is —CH₃ and abbreviated as Me,ethyl is —CH₂CH₃ and abbreviated as Et, isopropyl is —CH(CH₃)₂ andabbreviated as ^(i)Pr, tert-butyl is —C(CH₃)₃ and abbreviated as ^(t)Bu,tert-amyl is 1,1-dimethylpropyl, —C(CH₃)₂CH₂CH₃ and abbreviated as^(t)Am.

Structures A, B, C, D, E, F and G below illustrate novel imidazolatecompounds based upon these imidazoles.

In one embodiment, the present invention provides a metal compoundrepresented by Structure A:

wherein M is a metal selected from Group 8 to 16, including: Fe, Co, Ni,Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, In, Ge, Sn, Sb, Te, Bi; R¹ can be sameor different selected from group consisting of linear or branched C₁₋₁₀alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl; R²⁻³ are same or differentselected from group consisting of hydrogen, methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, isomers ofpentyl; R⁴⁻⁸ can be same or different selected from group consisting ofhydrogen, linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀aminoalkyl,

Representative examples of Structure A include, but are not limited to:

In another aspect, the present invention provides a metal compoundrepresented by Structure B:

wherein M is a metal selected from Group 4 to 16, including: Mn, Fe, Co,Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, In, Ge, Sn, Sb, Te, Bi; (n)=1, 2; R¹can be same or different selected from group consisting of linear orbranched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl; R²⁻³ can besame or different selected from group consisting of hydrogen, linear orbranched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl; (L) is aneutral coordinating ligand selected from ether, polyether, furans,amine, polyamine or alkoxyamine, pyridine, N-methylimidazole, olefin,diolefin, triolefin or polyolefin, alkyne, silylolefin, silyalkynecarbon monoxide, nitrile, isonitrile, silylnitrile or isocyanide, alkylphosphine, and aromatic phospine; (v) is 1-4; (X) is a mono anionselected from the group consisting of C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl,C₁₋₁₀ aminoalkyl, halides; alkoxy, hydride, amide, beta-diketonates,acetates, ketoiminates, diimines, alkoxides, amides, beta-ketoesters,amidinates, guanidinates, cyclopentadienyl, cyanide, isocyanide,pyrrolyl, formate, acetate, cyanate, oxalate, malonate, phenoxide,thiolate, trialkylsiloxide, bis(trialkylsilyl)amide, sulfide, nitrate,alkyl, silylalkyl, fluoroalkyl, aryl, hydride, pyrrolyl, and halide;m=0, 1; n=1, 2; (w)=2, 3; p=1, 2; such as:

In another aspect, the present invention provides a metal compoundrepresented by Structure C:

wherein M is a metal selected from Group 4 to 16, including; Ti, Zr, Hf,V, Nb, Ta, Cr, Mo, W, Al, In, Sn, Sb, Bi; (n) can be 1-6; R¹ can beselected from linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀aminoalkyl; R²⁻³ can be same or different selected from group consistingof hydrogen, linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀aminoalkyl; (X), (Y) and (Z) are mono anions, which can be the same orindividually different selected from alkoxy, beta-diketonates, acetates,ketoiminates, diimines, alkoxides, amides, hydrides, beta-ketoesters,amidinates, guanidinates, cyclopentadienyl, cyanide, isocyanide,pyrrolyl, formate, acetate, cyanate, oxalate, malonate, phenoxide,thiolate, trialkylsiloxide, bis(trialkylsilyl)amide, sulfide, nitrate,alkyl, silylalkyl, fluoroalkyl, aryl, hydride, pyrrolyl, and halide;exemplary alkoxy include, but not limited to; methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy,and tert-pentoxy; exemplary amides include, but not limited to;dimethylamide, diethylamide, ethylmethylamide; (b), (c) and (d) canindividually range from zero to 5, but (b)+(c)+(d)=(n)−1; (L) is aneutral coordinating ligand selected from ether, polyether, furans,amine, polyamine or alkoxyamine, pyridine, N-methylimidazole, olefin,diolefin, triolefin, polyolefin, alkyne, silylolefin, silyalkyne carbonmonoxide, nitrile, isonitrile, silylnitrile, isocyanide, alkylphosphine, aromatic phospine; (v) is 1-4; (p)=1, 2; n=3, 4, 5, 6; p=1,2; as illustrated by:

In another aspect, the present invention provides a metal compoundrepresented by Structure D:

wherein M is a metal selected from the lanthanide series, including; La,Ce, Py, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; (n)=2, 3 or4; R¹ can be selected from the group consisting of linear or branchedC₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, and C₁₋₁₀ aminoalkyl; R² and R³ can behydrogen, linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, and C₁₋₁₀aminoalkyl; (X) (Y) and (Z) are mono anions, which can be the same orindividually different selected from alkoxy, beta-diketonates, acetates,ketoiminates, diimines, alkoxides, amides, hydrides, beta-ketoesters,amidinates, guanidinates, cyclopentadienyl, cyanide, isocyanide,pyrrolyl, formate, acetate, cyanate, oxalate, malonate, phenoxide,thiolate, trialkylsiloxide, bis(trialkylsilyl)amide, sulfide, nitrate,alkyl, silylalkyl, fluoroalkyl, aryl, hydride, pyrrolyl, and halide;exemplary alkoxy include, but not limited to; methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy,and tert-pentoxy; exemplary amide include, but not limited to;dimethylamide, diethylamide, and ethylmethylamide; (b) and (c) canindividually range from zero to 2, but (b)+(c)+(d)=(n)−1; (L) is aneutral coordinating ligand selected from ether, polyether, furans,amine, polyamine, alkoxyamine, pyridine, N-methylimidazole, olefin,diolefin, triolefin, polyolefin, alkyne, silylolefin, silyalkyne, carbonmonoxide, nitrile, isonitrile, silylnitrile, isocyanide, alkylphosphine, aromatic phospine; (v) is 1-4; (p)=1, 2; as illustrated by:

In yet another aspect, the present invention provides a metal compoundrepresented by Structure E:

wherein M is a metal selected from the actinide series, including: Ac,Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr; (n)=2, 3, 4,5 or 6; R¹ can be selected from the group consisting of linear orbranched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, and C₁₋₁₀ aminoalkyl; R² andR³ can individually be hydrogen, linear or branched C₁₋₁₀ alkyls, C₁₋₁₀alkoxyalkyl, and C₁₋₁₀ aminoalkyl; (X) (Y) and (Z) are mono anions,which can be the same or individually different, selected from; alkoxy,beta-diketonates, acetates, ketoiminates, diimines, alkoxides, amides,hydrides, beta-ketoesters, amidinates, guanidinates, cyclopentadienyl,cyanide, isocyanide, pyrrolyl, formate, acetate, cyanate, oxalate,malonate, phenoxide, thiolate, trialkylsiloxide,bis(trialkylsilyl)amide, sulfide, nitrate, alkyl, silylalkyl,fluoroalkyl, aryl, hydride, pyrrolyl, and halide; exemplary alkoxyinclude, but not limited to; methoxy, ethoxy, n-propoxy, iso-propoxy,n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy, and tert-pentoxy;exemplary amide include, but are not limited to; dimethylamide,diethylamide, and ethylmethylamide; (b) and (c) can individually rangefrom zero to 2, but (b)+(c)+(d)=(n)-1; (L) is a neutral coordinatingligand selected from ether, polyether, furans, amine, polyamine oralkoxyamine, pyridine, N-methylimidazole, olefin, diolefin, triolefin orpolyolefin, alkyne, silylolefin, silyalkyne carbon monoxide, nitrile,isonitrile, silylnitrile or isocyanide, alkyl phosphine, and aromaticphospine; (v) is 1-4; (p)=1, 2.

In another aspect, the present invention provides a metal compoundrepresented by Structure F:

wherein M is a metal selected from Group 4 to 16, including; Fe, Co, Ni,Cr, Mn, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, In, Ge, Sn, Sb, Te, Bi, Ti, Zr,Hf, V, Nb, Ta, Cr, Mo, W, Al, In, Sn, Sb, Bi; La, Ce, Pr, Nd, Pm, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb; R¹ is selected from linear orbranched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, and C₁₋₁₀ aminoalkyl; R²⁻³ canbe same or different selected from group consisting of hydrogen, linearor branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, and C₁₋₁₀ aminoalkyl; atleast one of R¹, R² or R³ is an alkyl group; preferably R¹ is an alkylgroup; X is selected from the group consisting of alkoxy,beta-diketonates, acetates, ketoiminates, diimines, alkoxides, amides,hydrides, beta-ketoesters, amidinates, guanidinates, cyclopentadienyl,cyanide, isocyanide, pyrrolyl, formate, acetate, cyanate, oxalate,malonate, phenoxide, thiolate, trialkylsiloxide,bis(trialkylsilyl)amide, sulfide, nitrate, alkyl, silylalkyl,fluoroalkyl, aryl, hydride, pyrrolyl, and halide; n=0, 1, 2, 3; p=1, 2;exemplary alkoxy include, but not limited to; methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy,and tert-pentoxy; exemplary amide include, but not limited to;dimethylamide, diethylamide, and ethylmethylamide; exemplary alkylsinclude; methyl, ethyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, sec-butyl, tert-butyl, isomers of pentyl, and polyalkyl.

In another aspect, the present invention provides a metal compoundrepresented by Structure G:

wherein M is a metal selected from Group 4 to 16, including: Al, Sb, Bi,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; R¹ is selectedfrom linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, and C₁₋₁₀aminoalkyl; R²⁻³ can be same or different selected from group consistingof hydrogen, linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, andC₁₋₁₀ aminoalkyl; at least one of R¹, R² or R³ is an alkyl group;preferably R¹ is an alkyl group; R⁴ is selected from linear or branchedC₂₋₁₀ alkyl, C₆₋₁₀ aryl; X is selected from oxygen or NR⁵ wherein R⁵ isselected from linear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, andC₁₋₁₀ aminoalkyl; p=1.

In addition, there are also complexes, which contain two or more metals,but bimetallic is the most common case. Thus, these complexes aredescribed as N^((p+))P^((q+))(I)_(a)(X)_(b)(Y)_(c)(Z)_(d)(L)_(x) where Nand P are two different metals of oxidation states of (p+) and (q+),respectively. In these complexes, (p)+(q)=(a)+(b)+(c)+(d), whereas (x),(Y), (Z) and (L) are as described above.

The present invention is a metal imidazolate complex which can besubstituted in at least the 2-position, preferably in the 2 and 4 or 5position, preferably in the 2, 4 and 5 positions with a sufficientlybulky group, R, of the formula:

wherein the R¹, possibly R¹ and R² and possibly R¹, R² and R³ groupshave sufficient 3-dimensional form to impart a property to theimidazolate to bond with metal ions in a fashion that precludes theformation of a metal imidazolate polymer structures, but rather permitsmonomeric or dimeric metal compounds to form, which are volatile, havelow melting points and are readily soluble in solvents. R¹ can be abulky group, R² and R³ can be bulky groups or groups which are notbulky.

Preferably, the imidazolate's R¹, R² and R³ are individually selectedfrom the group consisting of methyl, ethyl, propyl, tert-butyl,isopropyl, tert-amyl, neopentyl, adamantyl, hexyl, cyclohexyl, propyl,butyl, isobutyl, pentyl, isopentyl, neopenty, norbornyl, andbicyclo[2.2.1]heptyl.

In some cases, the imidazolate R² group is methyl, ethyl, propyl orisopropyl.

Preferably, the imidazolate's R² and R³ are bulky groups.

The novel imidazolate compounds of the present invention are unique inthat they are formed from imidazolate anions, which are formed by thedeprotonation of imidazoles that are substituted in at least the 2position, preferably in the 2 and 4 or 5 position, more preferably inthe 2, 4 and 5 positions with alkyl groups that are sufficiently bulkyas to preclude the imidazolate anions from bridging multiple metalcenters to form polymeric involatile structures. Being thereby preventedfrom forming highly associated structures, they form monomeric ordimeric metal complexes, which are volatile.

Preferably, the imidazolate's R₁ is individually selected from the groupconsisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isopropyl,tert-amyl, neopentyl, adamantyl, hexyl, cyclohexyl, propyl, butyl,isobutyl, pentyl, cyclopentyl, isopentyl, neopenty, norbornyl,bicyclo[2.2.1]heptyl, dimethylbutyl, dimethylpentyl, dimethylhexyl, secbutyl, ethylmethylpropyl, isohexyl, and isopentyl; R¹ and R² can beselected from the group consisting of methyl, ethyl, propyl, isopropyl,tert-butyl, isopropyl, tert-amyl, neopentyl, adamantly, hexyl,cyclohexyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, isopentyl,neopenty, norbornyl, bicyclo[2.2.1]heptyl, dimethylbutyl,dimethylpentyl, dimethylhexyl, sec butyl, ethylmethylpropyl, isohexyl,and isopentyl.

Preferably, the imidazolate's R₂ is a hydrogen or a bulky group selectedfrom the group consisting of; hydrogen, methyl, ethyl; isopropyl,tert-butyl, isopropyl, tert-amyl, neopentyl, adamantyl, hexyl,cyclohexyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, isopentyl,neopentyl, norbornyl, bicyclo[2.2.1]heptyl, dimethylbutyl,dimethylpentyl, dimethylhexyl, sec butyl, ethylmethylpropyl, isohexyl,and isopentyl.

Most preferably, the imidazolate is:

-   2,4,5-tri-tert-butylimidazolate;-   2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate;-   2-(1,1-dimethylbutyl)-4,5-di-tert-butylimidazolate;-   2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpropyl)imidazolate;-   2,4,5-trimethylimidazolate;-   2-tert-butyl-4-methyl-5-ethylimidazolate;-   2-ethyl-4-methylimidazolate;-   2-isopropyl-4,5-di-tert-butylimidazolate;-   2-tert-butyl-4,5-di-isopropylimidazolate;-   2-isopropyl-4,5-di-tert-amylimidazolate;-   2-sec-butyl-4,5-di-tert-amylimidazolate; and,-   2-(1-ethyl-propyl)-4,5-di-tert-butylimidazolate,

and their metal complexes. Thus, by using sufficiently bulky groups,such as tert-butyl, when the imidazole is deprotonated to give an anion,it coordinates to a metal in an ‘eta-5’ mode, where the plane of thefive membered ring is positioned sideways to the metal ion. This thenpermits the metal to bond to all five atoms of the imidazolate ring, asshown in Formula B, where R represents bulky alkyl type groups.Additionally, the imidazolate anions of this disclosure can also bind ina novel ‘end on’ manner, as shown below in Formula C, where the bulkysubstituents permit the metal to bind only to to one of the imidazolatenitrogens. While not wishing to be bound by theory, it is alsoanticipated that other novel binding modes exist between the twoextremes of eta-5 and eta-1, where only two, three or four of theimidazolate ring atoms participate in bonding to the metal. Also,another mode of imidazolate coordination is shown in Formula D, whichpermits the formation of metal imidazolate dimer complexes.

Bulky groups for the purpose of the present invention are groups, whichhave sufficient 3-dimensional spacial form to create the sterichindrance, so that metals bonding with the imidazolates of the presentinvention are enabled to be preferably bonded in the ‘eta-5’ bonding orend on eta-1 bonding of Formulae B and C, respectively. Additionally,the bonding modes between these two extremes are also possible, such as;eta-2, eta-3 and eta-4.

Bulky groups can comprise C₃₋₁₂ groups, preferably branched alkyl,cyclic or aromatic, and optionally further derivatized with otherfunctional groups, such as; amine, hydroxyl, carboxylic, substitutedamine and similar derivatives. Alkanes, alkenes, alkynes, cyclic formsof the same, aromatics, and their derivatives are all contemplated asbulky groups, as long as they meet the requirement of having sufficientbulk in the form of 3-dimensional spacial form to induce ‘eta-5’ bondingof the imidazole with metals, or eta-4, or eta-3 or eta-2 or eta-1bonding to the metal. Other suitable bulky alkyl groups include, but notlimited to; methyl, ethyl, propyl, isopropyl, tert-amyl, neopentyl,adamantyl, hexyl, cyclohexyl, propyl, butyl, isobutyl, tertbutyl,pentyl, isopentyl, neopentyl, norbornyl, bicyclo[2.2.1]heptyl, nitro,C₉-C₂₀ alkylphenyl, C₁-C₁₀ alkoxy; alkylamine; and C₁-C₁₀ alkylfunctionalized with a heteroatom substituted ring structure selectedfrom the group consisting of imidazole, pyrrole, pyridine, furan,pyrimidine, pyrazole; C₁-C₁₀ alkyl functionalized with an amide group;C₁-C₁₀ alkyl functionalized with an ester group and mixtures thereof.

Thus, this disclosure teaches the synthesis of volatile metalimidazolate complexes, which use imidazole ligands, which aresubstituted in at least the 2 position.

Thus, in the present invention, when the bulky groups are characterizedby stating they impart a property to the imidazolate to bond with metalsin a ‘eta-5 bond’, or eta-1 bond, this does not preclude additionalbonding in linear fashion in addition to ‘eta-5’, but merely describes afavored or preferred bonding form. Without the bulky groups, theseimidazolates would not exhibit the propensity to favor ‘eta-5’ bonding(Formula B), or eta-1 bonding (Formula C) or the non-coplanar bridgingbonding (Formula D).

Unsubstituted phenyl, for instance, does not display sufficientbulkiness to be included in the definition of bulky groups, due to itslargely planar 3-dimensional shape, whereas, cyclohexane has sufficientbond angles to help constitute a bulky group.

In addition, these alkyl substituents can also be functionalized withcoordinating groups, such as; ether, amine, amide, cyano, isonitrile,imine, amidinine, ester, pyridine, imidazole, pyrrole, pyrazole,oxazole, isooxazole, furan, pyrimidine, furfuryl, oxirane, aziridine,oxolane, 1,3-dioxolane, 1,4-dioxane, 1,3,5-trioxane, pyrrolidine,piperidine, quinuclidine. They can also be functionalized with groupscapable of being deprotonated, so that with the imidazole also beingdeprotonated, they form dianions, which then can be coordinated to metalcenters. Such groups include, but are not limited to; cyclopentadiene,pyrrole, beta-diketone, beta-ketoimine, beta-diimine, alcohol, amine,amide, pyrrole, phenol, carboxylate, and amidinate.

The novel compounds of the present invention comprise anionic alkylfunctionalized imidazolate ligands, which are coordinated to transitionmetals, lanthanide metals, actinide metals, Group 1 and main groupmetals, including the chacogenides, to yield either monomeric or dimericcompounds, in addition to neutral ligand adducts of those compounds,which have exceptional thermal stability and clean evaporationcharacteristics.

The imidazolate anions used can also be asymmetrically alkylated toyield lower melting point compounds of high solubility, well suited todirect liquid injection (DLI). The structure of the ligand2,5-di-tertbutylimidazole, a new novel imidazole ligand createdaccording to this disclosure (see Example 1), is shown in FIG. 1. Alsoshown is the structure of 2,4,5-tri-tert-butylimidazole in FIG. 2.

Clean evaporation characteristics of these new metal complexes isespecially useful, since a low level of involatile residue is highlydesirable, as this translates to a controlled evaporation of the metalcomplex being possible, if it is used as a source precursor compound forALD or CVD processes. In addition, for CVD or ALD processes, many metalprecursors are dissolved in a solvent, and this solution is vaporized ina direct liquid injection (DLI) system. Basically, this comprisesdelivering a precisely controlled flow of solution into a vaporizer,where the solution and its dissolved solute are rapidly heated andvaporized under reduced pressure. The resulting vapor is thentransported into the CVD or ALD reactor. Typically, there areminaturized nozzles and narrow bore tubes used inside the vaporizer atthe point, where the solution is nebulized or simply introduced into thevaporization temperature. If the solute does not fully evaporate and aninvolatile residue is formed, these fine bore tubes can becomeobstructed, thereby preventing any further flow of solution. For thesereasons, it is highly desirable for the involatile residue observed inthe TGA experiment to be as low as possible to avoid the accumulation ofobstructing residues, for the best possible DLI performance. This isespecially important in a commercial manufacturing environment, wheresuch an equipment failure is prohibitively expensive.

The present invention is directed towards the use of substitutedimidazole ligands from which volatile monomeric or dimeric transitionmetal complexes can be synthesized. This is demonstrated by Examples 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 23, 25 and 26 for titaniumimidazolate compounds; Example 27 for zirconium; Examples 28 and 29 forcobalt; Example 30 for iron; Examples 31, 32, 33 and 34 for ruthenium;Example 36 for manganese; Example 39 for lanthanum; Example 40 forcerium, and Example 41 for europium.

In all of the above examples, an imidazole ligand is either directlyreacted with a metal halide (as in the case of titanium tetrachloride)or, is first deprotonated with a suitable base, such as n-butyl lithium,then reacted with a metal halide to ultimately give a metal imidazolatecompound. In some cases, the metal halide species contains only onehalide to be displaced by imidazole or imidazolate anion to yield thefinal product. Examples 12, 13, 14, 15, 16, 17, 18, 19, and 20demonstrate this, where imidazolate anion displaces chloride ion from(Cl)Ti(OR)₃, where R=OEt or OiPr (Et=ethyl; iPr=isopropyl). Similarly,Example 36 shows that2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate can displace bromideion from manganese pentacarbonyl bromide to give manganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)tricarbonyl. Inother cases, halide is displaced from a metal halide to yield a metalimidazolate compound still bearing halide which can then subsequently bedisplaced to form a new metal imidazolate compound.

Demonstrations of this approach are found in Examples 22 and 24, whereinitial displacement of chloride ion from TiCl₄ by2,4,5-tri-tert-butylimidazole or2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazole yieldstitanium(tBu₃imidazolate)trichloride andtitanium(tBu-tamyl₂imidazolate)trichloride, respectively. Thetitanium(tBu₃imidazolate)trichloride compound is then reacted withmethoxide ion to displace one (Example 25), then two (Example 26)chloride ions to yield titanium(tBu₃imidazolate)methoxide dichloride andtitanium(tBu₃imidazolate)dimethoxide chloride complexes, respectively.

Similarly, in Examples 28 and 29, cobalt dichloride is first reactedwith 2,4,5-tri-tert-butylimidazolate and2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate anions,respectively, to first displace one chloride ion to give theintermediates: cobalt(2,4,5-tri-tert-butylimidazolate) chloride andcobalt(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate) chloride,respectively. In both cases, the remaining chlorides are then displacedby the addition of cyclopentadieide anion to give the final products.

A similar strategy is found in Example 30, where2,4,5-tri-tert-butylimidazolate anion diplaces the first chloride ionfrom iron dichloride and the second chloride is then displaced withcyclopentadienide anion. Thus, it is clear that displacement of halideion from a transition metal halide is readily accomplished by reactionwith an imidazole ligand, or its imidazolate anion, to form a transitionmetal imidazolate complex. It is also clear that if there are remaininghalides in the metal imidazolate complex, they can be displaced by otherions to yield new and different imidazolate metal complexes. In thisway, imidazolate complexes of all the transition metals can be prepared,since metal halides for all of the transition metals exist.

Similarly, Examples 39, 40 and 41 illustrate that lanthanum triiodide,cerium triiodide and europium diiodide can be reacted with potassium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate) to yieldlanthanum(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)diiodidebis(tetrahydrofuran),cerium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)diiodidebis(tetrahydrofuran) and europium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate) iodidebis(tetrahydrofuran) respectively. Example 42 shows that europiumdiiodide can be reacted with potassium 2,4,5-tri-tert-butylimidazolateto yield di-europium tetra(2,4,5-tri-tert-butylimidazolate). Thus, sincehalide of all of the lanthanide elements exist, lanthanide imidazolatecomplexes can be synthesized. Similarly, actinide metal imidazolatecomplexes can be prepared from actinide metal halides.

Example 27 shows that zirconium tetra(dimethylamide) can be reacted with2,4,5-tri-tert-butylimidazole to yield zirconium(2,4,5-tri-tert-butylimidazolate)tri(dimethylamide). Therefore, metalimdazolates are readily prepared by the reaction of metal amidecompounds with the imidazole ligands of this disclosure.

The present invention is directed to the synthesis and use of new andnovel and volatile Group 3-16 transition metal, lanthanide metal,actinide metal and main group metal complexes, including thechalogenides of alkylated imidazolate-based compounds and theirsolutions for vapor delivery upon direct liquid injection, wherein thealkyl groups of the imidazolate ligand anion can be bulky hydrocarbons,such as: tert-butyl, tert-amyl, etc.; and can be nitrogen or oxygencontaining alkyl, such as: methyl, ethyl, propyl, isopropyl, tertiaryamine or ether groups. Additionally, these new compounds can alsocoordinate with other neutral ligands, such as: ethers or amines oralkoxyamines

The present invention also includes a novel method of synthesizing themetal compounds by direct metallization of the imidazolate ligands usinga metal reagent, such as a metal hexamethyldisilazane, metal alkoxide,metal hydroxide or metal hydride, thereby providing an efficientalternative to using the standard metathesis type of reaction, where theimidazole is first treated with a metal hydride, such as sodium hydride,to form a sodium imidazolate, which is then in turn reacted with a metalhalide, such as iodide.

Other novel techniques for synthesizing these new compounds include, butare not limited to, direct reaction of the imidazole ligands with metal,etc., in the presence or absence of added reagents, such as ammonia, orby reacting the imidazole ligands with metal vapor. The novel compoundsmay also be prepared by electrochemical syntheses.

Additionally, a wide variety of metals and metalizing agents can be usedto effectively deprotonate the imidazole ligands prior to reacting witha source of the metal of the final complex. Such deprotonating reagentsinclude, but are not limited to: n-butyl lithium, n-hexyl lithium,sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide,potassium hydride, sodium hydride, sodium metal, sodium amide, potassiummetal, potassium amide, barium metal, sodium t-butoxide, potassiumt-butoxide, alkyl and aryl Grignard reagents. Metal sources include, butare not limited to: metal iodide, metal bromide, metal chloride, metaltrifluoromethlysulfonate, metal trifluoroacetate, metalhexafluoroacetylacetone, metal trifluoroacetylacetonate, metalacetyacetonate, metal diimine, metal ketoimine, metal amidinate, metalguanidinate, metal amide, metal alkoxide, metal amide, metal carbonate,metal acetate, metal carbonate, metal formate, metal propionate, metalphenoxide and metal hydroxide.

Mixed complexes can also be created, where the alkyl based imidazolesubstituents are varied differently among imidazolate anions, and thenthis mixture is complexed to a metal (M). Thus, if two differentimidazolate anions I¹ and I² are mixed together, and then complexed to ametal to satisfy two of its valencies (it could be of a valency higherthan two, but the remaining valencies are satisfied by othercorrdinating anions), three unique metal complexes can be made; i.e.M(I¹)₂, M(I¹I²), and M(I²)₂. If three different imidazolate anions I¹,I² and I³ are mixed, and then complexed to M, six metal complexes areformed; i.e., M(I¹)₂, M(I¹I²), M(I¹I³), M(I²)₂, M(I²I³) and M(I³)₂.These mixtures will be either liquids or highly soluble formulations forDLI. This same logic can also be applied to making metal complexes froma mixture of four, five or six imidazole ligands. Also, the groups R¹⁻³of one imidazolate anion can be joined to the R¹⁻³ groups of anotherimidazolate anion to connect the two anions together. The neutral ligand(L) is selected from aliphatic C₁-C₂₀ ether or polyether, crownethers,such as 18-crown-6, amine or polyamine, alkoxyamine or polyalkoxyamine,amide or polyamide, ester or polyester, aromatic ether, aromatic ester,aromatic amide, aromatic amine, pyridine, imidazole, pyridine, pyrazine,furan, alkylcarbonate, pyrrole, trialkylphosphine or triarylphospine.Additionally, groups R¹, R², R³ and can be linked together to form ringstructures, These ring structures can also be aromatic.

Several advantages can be achieved through these metal-containingpolyalkylated imidazole based compounds as precursors for chemical vapordeposition or atomic layer deposition, and these include:

an ability to form reactive complexes in good yield;

an ability to form monomeric or dimeric thermally stable complexes,coordinated with one kind or mixed kinds of ligand, thus achievinghigher a capability to form highly conformal metal oxide thin films,suited for use in microelectronic devices;

an ability to enhance the surface reaction between the metal-containingalkylated imidazolate anion and the surface of a substrate due to thehigh chemical reactivity of the complexes; and,

an ability to tune the physical properties of these metal-containingpolyalkyl imidazole anions via a change in the alkyl substituent groups.

Additionally, metal complexes can also be made by coordinating twodifferent polyalkylated imidazolate anions to a metal center, such thatthe two ligands experience an optimal ‘fit’ or ‘interlock’ with eachother and around the metal in such a way as to provide an adequatecoordination sphere to create a stable monomeric or dimeric complex.

While not wishing to be bound by theory, the molecules of thisdisclosure are excellent precursors for use in CVD or ALD processes fordepositing metal oxide containing films, by reacting them together,either sequentially or simultaneously, with an oxidizer, such as: water,hydrogen peroxide, alcohol, oxygen, ozone, nitrous oxide, nitrogendioxide or combinations thereof. Additionally, the metal precursormolecules of this disclosure can be used in a CVD, pulsed CVD or ALDmode to deposit metal containing films, including metal nitrides byreacting with nitrogen sources, such as amines or ammonia.Alternatively, metallic films may be formed by reacting with a suitablereducing agent, such as hydrogen.

In one embodiment, the present invention is a metal compound of theformula: (M^((n+)))_(z)(I)_(a)(X)_(b)(Y)_(c)(Z)_(d)(L)_(x) where (I)represents an alkylated imidazolate anion having the formula:

and (M) is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe,Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re,Os, Ir, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy nHo, Er, Tm,Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr, Li,Na, K, Rb, Cs, Fr, Al, Ga, In, TI, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se,Te, Po and mixtures thereof; where (n) is 1-6; (z) is one or two; a, b,c, d, n and z are selected to make the metal complex electroneutral, andwhen X, Y and Z are monoanions then (a)+(b)+(c)+(d)=(z)×(n); when (a) isgreater than 1, each imidazolate anion can be different; (L) is aneutral ligand selected from the group consisting of aliphatic C₁-C₂₀ether or aminoether, polyether; crownether, crown aminoether; amine;

poly amine; amide; poly amide; ester; polyester; aromatic ether;aromatic ester; aromatic amide; aromatic amine; pyridine; imidazole;pyridine; pyrazine; furan; pyrrole, olefin, diolefin, triolefin,polyolefin, alkyne, silylolefin, silyalkyne, carbon monoxide, nitrile,silylnitrile or isocyanide, alkyl phosphine, and aromatic phospine; (x)is 1-5; (X), (Y) and (Z) are individually selected from the groupconsisting of: beta-diketonates, ketoiminates, diimines, alkoxides,amides, amidines, hydrides, beta-ketoesters, amidinates, guanidinates,cyclopentadienyl, cyanide, isocyanide, formate, acetate, oxalate,malonate, phenoxide, thiolate, trialkylsiloxide,bis(trialkylsilyl)amide, sulfide, nitrate, alkyl, silylalkyl,trialkylsiloxide, fluoroalkyl, aryl, hydride, pyrrolyl, polyalkylatedpyrrolyl anion, halide and mixtures thereof; and R¹⁻³ are individuallyselected from the group consisting of H, C₁₋₁₂, wherein at least one ofR¹⁻³ is C₁₋₁₂, and C₁₋₁₂ can be substituted. The C₁₋₁₂ is selected fromthe group consisting of normal and branched alkyl, normal and branchedalkenyl, normal and branched alkynyl, aromatic and heteroatomderivatized compounds of the preceding groups, that is, substituted.Substitution can be with nitrogen atoms, oxygen atoms and otherheteroatoms, forming such groups as amine, ether, alcohol, carboxy,ketone, and similar heteroatom substitutions.

Preferably, R¹ is C₁₋₁₂, and C₁₋₁₂ can be substituted. More preferably,R¹ and R² are C₁₋₁₂, and C₁₋₁₂ can be substituted. Still morepreferably, R¹, R² and R³ are C₁₋₁₂, and C₁₋₁₂ can be substituted.Preferably, at least one of R¹⁻³ is tertiary alkyl, independentlyselected from tert-butyl and tert-amyl.

In one embodiment, the metal compound of the present invention isselected from the group consisting of Mn(I)(CO)₃, Ti(I)(O^(i)Pr)₃,Ti(I)(OEt)₃, Ti(I)(NMe₂)₃, Ti(I)(NMeEt)₃, Ti(I)Cl₃, Zr(I)Cl₃, Zr(I)₂Cl₂,Zr(I)(OEt)₃, Zr(I)(NMe₂)₃, Zr(I)₂(OEt)₂, Zr(I)₂(O^(i)Pr)₂,Zr(I)₂(NMe₂)₂, Fe(I)(C₅R₅), Ru(I)(C₅R₅), Co(I)(C₅R₅), Ln(I)(X)₂ (L)₂,Ln(I)(X)(L)₂, wherein R is independently selected from hydrogen, methyl,ethyl, n-propyl, and iso-propyl, (X) can be halide, (L) is a neutralligand.

A preferred list of the compounds of the present invention includesmetal compounds wherein imidazolate anion is independently selected from2,4,5-tri-tert-butylimidazolate;2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate;2-(1,1-dimethylbutyl)-4,5-di-tert-butylimidazolate;2-(1,1-dimethylbutyl)-4,5-di-(1,1-dimethylpropyl)imidazolate;2,4,5-trimethylimidazolate; 2-tert-butyl-4-methyl-5-ethylimidazolate;2-ethyl-4-methylimidazolate; 2-isopropyl-4,5-di-tert-butylimidazolate;2-tert-butyl-4,5-di-isopropylimidazolate;2-isopropyl-4,5-di-tert-amylimidazolate;2-sec-butyl-4,5-di-tert-amylimidazolate; and,2-(1-ethyl-propyl)-4,5-di-tert-butylimidazolate.

Preferably, the metal compound of the present invention is selected fromthe group consisting of titanium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)triethoxide;titanium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)triiso-propoxide;titanium(2,4,5-trimethylimidazolato)triisopropoxide;titanium(2-ethyl-4-methyl-imidazolate)triisopropoxide; di-titaniumbis(2,5-di-tert-butyl-imidazolate)hexaethoxide; titanium(2-isopropyl-4,5-di-(1,1-dimethylpropyl)imidazolate)triisopropoxide;di-titanium bis(2,4-di-tert-butylimidazolate)hexaisopropoxide; titaniumbis(2,5-di-tert-butylimidazolate)diisopropoxide;titanium(2,4,5-tri-tert-butylimidazolate)triisopropoxide; titanium(2-tert-butyl-4,5-di(1,1-dimethylpropyl)limidazolate)-triisopropoxide;titanium(2,4,5-tri-tert-butyl-imidazolate)trichloride; titanium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)trichloride;titanium (2,4,5-tri-tert-butyl-imidazolate)dichloride methoxide;titanium(2,4,5-tri-tert-butyl-imidazolate) chloride dimethoxide;zirconium(2,4,5-tri-tert-butyl imidazolate)tri(dimethylamide);cobalt(2,4,5-tri-tert-butylimidazolate)(cyclopentadienide); cobalt(2-tert-butyl-4,5-di(1,1-dimethylpropyhimidazolate)(cyclopentadienidel);iron (2,4,5-tri-tert-butylimidazoate)(cyclopentadienide); ruthenium(2,4,5-trimethylimidazolate)(pentamethylcyclopentadienide); ruthenium(2-ethyl-4-methylimidazolate)(pentamethylcyclopentadienide); ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(pentamethylcyclopentadienide);ruthenium (2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(pentamethylcyclopentadienide);ruthenium(pentamethylcyclopentadienide)(imidazolate);manganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate)tricarbonyl;lanthanum (2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)diiodidebis(tetrahydrofuran); andcerium(2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazolate diiodidebis(tetrahydrofuran).

In one embodiment, the present invention is a metal compound of theformula M^((n+))(I)_(a)(X)_(b)(Y)_(c)(Z)_(d)(L)_(x) where (I) is animidazolate based dianion having the formula:

functionalized with an acidic group which acidic group is deprotonated,the acidic group selected from the group consisting of; an alcohol, anamine, an amide, a carboxylate, a beta-diketone, a beta-diimimine, acyclopentadiene, and a pyrrole anion, wherein when (a)=1 then(a)+1+(b)+(c)+(d)=(n) and wherein when (a)=2 then (a)+2+(b)+(c)+(d)=(n);and (X), (Y) and (Z) are individually selected from the group consistingof: beta-diketonates, ketoiminates, diimines, alkoxides, amides,amidines, hydrides, beta-ketoesters, amidinates, guanidinates,cyclopentadienyl, cyanide, isocyanide, formate, acetate, oxalate,malonate, phenoxide, thiolate, trialkylsiloxide,bis(trialkylsilyl)amide, sulfide, nitrate, alkyl, silylalkyl,trialkylsiloxide, fluoroalkyl, aryl, hydride, pyrrolyl, polyalkylatedpyrrolyl anion, halide and mixtures thereof; and R¹⁻³ are individuallyselected from the group consisting of H, C₁₋₁₂, wherein at least one ofR¹⁻³ is C₁₋₁₂, and C₁₋₁₂ can be substituted.

In yet another embodiment, the present invention is a metal compound,which contains two metals, of the formulaN^((p+))P^((q+))(I)_(a)(X)_(b)(Y)_(c)(Z)_(d)(L)_(x) where N and P aretwo different metals of oxidation states (p+) and (q+), respectively;wherein (p)+(q)=(a)+(b)+(c)+(d); and (X), (Y) and (Z) are individuallyselected from the group consisting of: beta-diketonates, ketoiminates,diimines, alkoxides, amides, amidines, hydrides, beta-ketoesters,amidinates, guanidinates, cyclopentadienyl, cyanide, isocyanide,formate, acetate, oxalate, malonate, phenoxide, thiolate,trialkylsiloxide, bis(trialkylsilyl)amide, sulfide, nitrate, alkyl,silylalkyl, trialkylsiloxide, fluoroalkyl, aryl, hydride, pyrrolyl,polyalkylated pyrrolyl anion, halide and mixtures thereof; and where (I)represents an alkylated imidazolate anion having the formula:

and R¹⁻³ are individually selected from the group consisting of H,C₁₋₁₂, wherein at least one of R¹⁻³ is C₁₋₁₂, and C₁₋₁₂ can besubstituted.

The present invention is also a process where a metal compound of theabove compounds is used as a volatile precursor for the deposition ofmetal containing thin films by a process selected from the groupconsisting of ALD, CVD, PECVD, pulsed CVD and molecular layerdeposition; over a temperature range of 0° C. to 1000° C. and a pressureof 0.1 Torr to 1 atmosphere.

Another embodiment is a process using the metal compounds describedabove to grow thin metal containing films by spinning a solution of themonto a substrate and then reacting the resulting layer of precursor togive the desired metal containing film.

Additionally, the present invention is a process where a metal compounddescribed above is used as volatile precursors for the growth of phasechange alloys by the processes selected from the group consisting ofALD, CVD, PECVD, pulsed CVD, and Molecular layer Deposition.

More preferably, he process is wherein thin films are grown bydeposition from a solution of these precursors in a super criticalfluid. Preferably, the super critical fluid is carbon dioxide.

In another embodiment, the present invention is a process using a metalcompound of the above descriptions wherein the process is selected fromthe group consisting of ALD, CVD, pulsed CVD, PECVD, and molecular layerdeposition; using a reactor pressure between 0.001-1000 Torr; atemperature from 0-1000° C.; reacting the metal compound with an oxidantselected from the group consisting of water, alcohol, oxygen, ozone,nitrous oxide, nitrogen dioxide, hydrogen peroxide and combinationsthereof, to grow a metal oxide containing film.

In an alternate of the above process, the present invention is a processusing a metal compound described above, wherein the process is selectedfrom the group consisting of ALD, CVD, pulsed CVD, PECVD, and molecularlayer deposition; using a reactor pressure between 0.001-1000 Torr; atemperature from 0-1000° C.; by reacting the metal compound with areagent of nitrogen source molecules selected from the group consistingof ammonia, amines and mixtures thereof.

The present invention is also a method of synthesizing the metalcompounds described above by direct metallization of the imidazoleligands using a metal reagent selected from the group consisting ofn-butyl lithium, n-hexyl lithium, sec-butyl lithium, tert-butyl lithium,lithium diisopropylamide, potassium hydride, sodium hydride, sodiummetal, potassium metal, sodium t-butoxide, and potassium t-butoxide; andthen reacting the resulting product with a compound selected from thegroup consisting of metal iodide, metal acetate, metal carboxylate,metal carbonate, metal formate, metal bromide, metal trifluoroacetate,metal hexafluoroacetylacetone, metal trifluoroacetylacetonate, metalacetyacetonate, metal diimine, metal ketoimine, metal amidinate, metalguanidinate and mixtures thereof.

Alternately, the present invention is a method of directly synthesizingcompounds of the descriptions above by reacting a an alkylated imidazoleusing a a compound selected from the group consisting of metal amide,metal phenoxide, metal hydroxide, metal alkyl, metal aryl and mixturesthereof.

In yet another embodiment the present invention is a method ofsynthesizing the metal compounds described above by reaction of theimidazole ligand with metal in the presence of ammonia.

A further embodiment is a process of dissolving a metal compounddescribed above in a suitable solvent, and injecting a resultingsolution into a direct liquid injection system for flash vaporization ofthe precursor and solvent and delivering a resulting vapor stream into areactor for the growth of metal containing films by a process selectedfrom the group consisting of; ALD, CVD, pulsed CVD, PECVD and MolecularLayer Deposition.

EXAMPLES Example 1 Synthesis of 2,5-di-tert-butylimidazole

5.44 g (0.04 moles) of 2,2-dimethylpropanimideamide hydrochloride weremixed with 7.2 g (0.04 moles) of 1-bromopinacolone and 11.2 g oftriethylamine in 16.0 g of diethylformamide (DEF) and stirred at roomtemperature for 7 days. The reaction mixture was then poured into waterand extracted three times with 50 ml units of hexane. The hexanefractions were combined and washed three times with 50 ml aliquots ofwater. The hexane layer was then stirred with 5 g of anhydrous magnesiumsulfate over night. The hexane was then removed by vacuum down to avolume of 5 ml to yield a fine suspension. This was filtered and theresulting solid washed with fresh hexane to yield 4.22 g (59%theoretical) of colorless fine crystalline product, 99% pure by GasChromatography Mass Spectrometry gave a parent ion at 180 amu. Structureconfirmed by X-ray crystallography (see FIG. 1)

¹H NMR: (500 MHz, D₈ THF): δ=1.23 (s, 9H), b=1.3 (s, 9H), b=6.48 (s,1H), b=10 (bs, 1H).

¹H NMR: (500 MHz, D₈ THF): δ=30.3 (s, 3C), δ=30.8 (s, 3C), δ=32.1 (s,1C), δ=33.6 (s, 1C), δ=111 (bs, 1C), δ=148 (bs, 1C), δ=155 (s, 1C).

Example 2 Synthesis of 2,2,5,5-tetramethyl-3,4-hexanedione

26.44 mL (0.240 moles) 2-chloro-2-methyl propane was slowly added to5.76 g, (0.240 moles) of magnesium turnings in 240 mL of tetrahydrofuranto make the Grignard reagent, t-BuMgCl. The freshly prepared Grignardreagent was slowly added to a mixture of 34 g (0.240 moles) copperbromide and 41 g (0.480 moles) of lithium bromide in 270 mL oftetrahydrofuran (THF), cooled to −65° C. 8.72 mL (0.10 moles) of oxalylchloride in 30 mL of THF was then added slowly, maintaining mixturetemperature at −65° C. The resulting mixture was stirred for an hour at−65° C., then warmed up to room temperature overnight. 90% of the THF isremoved by vacuum, followed by the addition of 500 ml of hexane and 300ml of a saturated aqueous solution of ammonium chloride. The hexanelayer was separated and the aqueous layer extracted with three 200 mllots of hexane. The hexane layers were then combined and washed withwater prior to drying with 10 g of anhydrous magnesium sulfate. Themixture was then filtered and the hexane distilled off under atmosphericpressure to yield the product as a yellow oil. Yield=10.5 g (53% oftheoretical)

Mass spectrum: 170 mu (parent ion).

Example 3 Synthesis of 2,4,5-tri-tert-butylimidazole

1.6 g (0.0094 moles) of 2,2,5,5-tetramethyl-3,4-hexanedione were mixedwith 2.9 g (0.037 moles) of ammonium acetate, 3.4 g (0.057 moles) ofacetic acid and 1.6 g (0.019 moles) of pivaldehyde and heated to 13° C.for 72 hrs in a sealed container. This mixture was then cooled andslowly added to an excess of aqueous saturated sodium bicarbonatesolution. The resulting mixture was extracted with 3×50 ml of hexane.The hexane fractions were combined, washed three time with 20 mlaliquots of pure water, then dried over anhydrous sodium sulfate.Evaporation of hexane yielded crude 2,4,5-tri-tert-butylimidazole as itshydrate (two molecules of imidazole per water molecule). To dry thisproduct, it was then refluxed in excess hexamethyldisilazane for 48 hrs.The hexamethyldisilazane and hexamethyldisiloxane (formed from thedrying process) was then evaporated, and the resulting solid sublimed at60° C. to give colorless crystals, yield 1.3 g (58% of theoretical).

¹H NMR: (500 MHz, C₆D₆): δ=1.24 (s, 9H), δ=1.26 (s, 9H), δ=1.65 (s, 9H),δ=8.07 (bs, 1H).

¹³C NMR: (500 MHz, C₆D₆): δ=30.0 (s, 3C), δ=31.70 (s, 1C), δ=32.26 (s,3C), δ=32.87 (s, 1C), δ=33.18 (s, 3C), δ=34.07 (s, 1C), δ=130.16 (s,1C), δ=143.84 (s, 1C), δ=149.21 (s, 1C).

Mass spectrum: 236 mu (parent ion). Structure confirmed by singlecrystal X-ray analysis, see FIG. 2.

Example 4 Synthesis of 3,3,6,6-tetramethyl-4,5-octanedione

2-chloro-2-methyl butane (96 mL, 0.78 mol) was slowly added to magnesiumpellets under a blanket of nitrogen, 18.72 g, (0.78 moles) of magnesiumturnings in 780 ml of tetrahydrofuran were activated by the addition of0.5 ml of 1,2-dibromoethane. 2-chloro-2-methyl butane (96 mL, 0.78 mol)were then slowly added resulting in the gradual formation of Grignardreagent, accompanied by a reaction exotherm. This Grignard reagent wasthen slowly added to a mixture of 112 g (0.78 mol) of copper bromide and67 g (0.78 mol) of lithium bromide dissolved in 340 mL ofterahydrofuran, cooled to −65° C. After all the Grignard was added andthe temperature stabilized at −65° C., 26 mL (0.30 mol) of oxalylchloride in 100 mL of THF was added slowly, maintaining mixturetemperature at −65° C. The resulting mixture was stirred for an hour at−65° C., then warmed up to room temperature overnight. 90% of the THFwas then removed by vacuum. 500 ml of hexane and 300 mL of saturatedaqueous ammonium chloride were then added to the resultant slurry andthe hexane layer separated. The aqueous layer was then further extractedwith three 200 ml lots of hexane. The combined hexane layers were thenwashed with 200 mL of water, then dried over 10 g of anhydrous magnesiumsulfate for one hour. The magnesium sulfate was then filtered off, andthe hexane distilled off at atmospheric pressure to yield the crudeproduct diketone as an orange red liquid. Yield=32.2 g (54% oftheoretical).

Mass spectrum: 198 mu (parent ion).

Example 5 Synthesis of2-tert-butyl-4,5-di-(1,1-dimethylpropyl)limidazole

A mixture of 32.3 g (0.163 mol) of 3,3,6,6-tetramethyl-4,5-octanedione,50 g (0.652 mol) of ammonium acetate, 36 mL (0.326 mol) of pivaldehyde(36 mL, 0.326 mol) and 56 mL (0.978 mol) of acetic acid was heated to200° C. in a sealed stainless steel vessel for 3 days. The resultingproduct mixture was neutralized with sodium bicarbonate solution, thenextracted with four 200 ml lots of hexane. The combined hexane layerswere washed 3× with 100 mL of water then 100 ml of satuared sodiumchloride solution. 10 g of anhydrous magnesium sulfate was added andstirred overnight. Filtration followed by removal of hexane by vacuumyielded the crude product as a yellow oil. Yield 31.5 g (73% oftheoretical).

Mass spectrum: 264 mu (parent ion).

Example 6 Synthesis of2-iso-propyl-4,5-di-(1,1-dimethylpropyl)limidazole

A mixture of 60.0 g (0.303 mol) of 3,3,6,6-tetramethyl-4,5-octanedione,140.2 g (1.818 mol) of ammonium acetate, 32.78 g (0.455 mol) ofisobutyraldehyde and 163.77 g (2.727 mol) of acetic acid was heated at180° C. in a sealed stainless steel vessel for 2 days. The resultingproduct mixture was neutralized with sodium bicarbonate solution, thenextracted with two 200 ml lots of hexane. The combined hexane layerswere washed 2× with 200 mL of water then 100 ml of satuared sodiumchloride solution. 10 g of anhydrous magnesium sulfate was added andstirred overnight.

Filtration followed by removal of hexane by vacuum yielded the crudeproduct as a light yellow liquid. The liquid was purified by vacuumdistillation at 85° C. (0.3 torr) to yield 42.7 g of2-iso-propyl-4,5-di-tert-amylimidazole, mp ˜28° C. (56% yield).

Mass spectrum: 250 mu (parent ion).

Example 7 Synthesis of 2-tert-butyl-4-methyl-5-ethyl-imidazole

A mixture of 23.65 g (0.275 mol) of pivaldehyde, 77.1 g (1.000 mol) ofammonium acetate, and 90.10 g (1.500 mol) of acetic acid was chargedinto 500 ml flask equipped with addition funnel. The mixture was heatedto 90-95° C. and 25.0 g (0.25 mol) of 2,3-pentanedione was added fromthe addition funnel within ˜20 minutes. The mixture was heated for 2hours at 110° C. and cooled to room temperature (RT). The resultingproduct mixture was extracted with 300 ml of hexane to remove oxazolederivatives. The remaining fraction was neutralized with sodiumbicarbonate solution. The product was extracted with 2×150 ml of diethylether. The combined ether layers were washed with 2×100 mL of water then100 ml of saturated sodium chloride solution. 10 g of anhydrousmagnesium sulfate was added and stirred overnight. Filtration followedby removal of ether by vacuum yielded the crude product as a yellowsolid. The material was purified by vacuum sublimation to yield 4.0 g of2-tert-butyl-4-methyl-5-ethyl-imidazole (56 yield).

Mass spectrum: 166 mu (parent ion).

Example 8 Synthesis of 2-sec-butyl-4,5-di-tert-butylimidazole

A mixture of 10.0 g (0.059 mol) of 2,2,5,5-tetramethyl-3,4-hexanedione,27.2 g (0.353 mol) of ammonium acetate, 7.6 g (0.088 mol) of2-methylbutyraldehyde and 42.4 g (0.706 mol) of acetic acid was refluxedunder nitrogen atmosphere for 16 hours. The resulting product mixturewas neutralized with sodium bicarbonate solution, then extracted withtwo 200 ml lots of hexane. The combined hexane layers were washed with2×100 mL of water then 2×100 ml of satuared sodium chloride solution. 10g of anhydrous magnesium sulfate was added and stirred overnight.Filtration followed by removal of hexane by vacuum yielded 8.5 g ofcrude product as a light yellow solid. The solid was purified by vacuumsublimation to yield 6.3 g of white solid (46% isolated yield).

Mass spectrum: mu 236 (parent ion).

Example 9 Synthesis of 2-(1-ethyl-propyl)-4,5-di-tert-butylimidazole

A mixture of 15.0 g (0.088 mol) of 2,2,5,5-tetramethyl-3,4-hexanedione,51.0 g (0.661 mol) of ammonium acetate, 17.8 g (0.178 mol) of2-ethylbutyraldehyde and 60.38 g (1.001 mol) of acetic acid was refluxedunder nitrogen atmosphere for 44 hours. The resulting product mixturewas neutralized with sodium bicarbonate solution, then extracted withtwo 200 ml lots of hexane. The combined hexane layers were washed with2×150 mL of water then 3×200 ml of satuared sodium chloride solution. 10g of anhydrous magnesium sulfate was added and stirred overnight.Filtration followed by removal of hexane by vacuum yielded 17.7 g ofcrude product as a light yellow solid. The solid was purified by vacuumtransfer to yield 15.1 g of white solid (68.5% isolated yield).

Mass spectrum: mu 250 (parent ion).

Example 10 Synthesis of 2,5-dimethyl-3,4-hexanedione

275 ml of 2 M solution of isopropylmagnesium chloride in tetrahydrofuranwas then slowly added to a mixture of 78.90 g (0.55 mol) of copperbromide and 47.77 g 0.550 mol) of lithium bromide dissolved in 600 mL ofTHF, cooled to −65° C. After all the Grignard was added and thetemperature stabilized at −65° C., 21.8 ml (0.250 mol) of oxalylchloride in 100 mL of THF was added slowly, maintaining mixturetemperature at −65° C. The resulting mixture was stirred for an hour at−65° C., then warmed up to room temperature overnight. 90% of the THFwas then removed by vacuum. 300 ml of hexane and 100 mL of saturatedaqueous ammonium chloride were then added to the resultant slurry andthe hexane layer separated. The aqueous layer was then further extractedwith two 100 ml lots of hexane. The combined hexane layers were thenwashed with 2×200 ml of 2 M HCl, 20 ml of 10% NaHCO₃ and 2×200 ml of 25%NaCl solution, then dried over 10 g of anhydrous magnesium sulfate forone hour. The magnesium sulfate was then filtered off and the hexanedistilled off at atmospheric pressure to yield the crude productdiketone as an orange red liquid. The product was purified by vacuumdistillation to obtain 3.2 g of orange liquid (9% yield).

Mass spectrum: 141 mu (parent ion).

Example 11 Synthesis of 2-tert-butyl-4,5-iso-propyl-imidazole

A mixture of 2.5 g (mol) of 2,5-dimethyl-3,4-hexanedione, 6.5 g (mol) ofammonium acetate, 2.1 g (0.178 mol) of pivaldehyde and 7.6 g (mol) ofacetic acid was refluxed under nitrogen atmosphere for 4 hours. Theresulting product mixture was neutralized with sodium bicarbonatesolution, then extracted with 50 ml of diethyl ether. Organic fractionwas analyzed by GC-MS to confirm the formation of2-tert-butyl-4,5-iso-propyl-imidazole.

Mass spectrum: mu 208 (parent ion).

Example 12 Synthesis of titanium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)triethoxide

To a solution of 5.11 g (18.90 mmol)2-tert-butyl-4,5-di-tert-amyl-imidazolate lithium salt in 50 mL ofhexanes at −40° C. was added a solution of 4.13 g (18.90 mmol)TiCl(OEt)₃ in 25 mL of hexanes at −40° C. drop-wise. Upon addition, thereaction mixture became dark brown in color. The reaction was refluxedfor 16 hours after which it was stopped, cooled, and an orange solid wasfiltered off weighing 0.48 g. The filtrate was pumped under vacuum to aviscous dark brown oil weighing 8.88 g. The crude product can be furtherpurified by vacuum distillation.

hu 1H-NMR (500 MHz, C₆D₆) δ (ppm): 4.18 (q, 6H, OCH₂CH₃), 1.92 (q, 4H,imid), 1.67 (s, 12H, imid), 1.67 (s, 9H, imid), 1.08 (t, 9H, OCH₂CH₃),0.85 (t, 6H, imid).

Example 13 Synthesis oftitanium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)tri-iso-propoxide

Method A: To a solution of 5.00 g (19.19 mmol) TiCl(OPr^(i))₃ in 30 mLof THF at −78° C. was added 5.19 g (19.19 mmol) of2-tert-butyl-4,5-di-tert-amyl-imidazolate lithium salt synthesized insitu. The reaction was refluxed for 16 hours after which all volatileswere removed under vacuum. The resulting waxy amber-colored solid waspartially dissolved in hexanes and a white solid was filtered offweighing 2.32 g. The filtrate was pumped under vacuum to a viscous darkamber-colored oil weighing 8.51 g. The crude product can be furtherpurified by vacuum distillation. The crude yield was 91%.

hu 1H-NMR (500 MHz, C₆D₆) δ (ppm): 4.50 (sept, 3H, OCH(CH₃)₂), 1.96 (q,4H, imid), 1.69 (s, 12H, imid), 1.69 (s, 9H, imid), 1.13 (d, 18H,OCH(CH₃)₂), 0.84 (t, 6H, imid).

Method B: Under a blanket of dry nitrogen, 5.28 g (20 mmoles) of2-tert-butyl-4,5-di-tert-amylimidazole) dissolved in 50 ml of dry THFwere added, with stirring, to 0.8 g of potassium hydride (20 mmoles) in50 ml of THF. After 20 minutes the evolution of hydrogen ceased leavinga clear solution. This was then added to 5.21 g (20 mmoles) ofchlorotriisopropoxytitanium dissolved in 20 ml of THF at roomtemperature. The resulting mixture was then stirred for four hours atroom temperature, after which the solvent was removed by the applicationof vacuum, 200 ml of hexane were added to dissolve the crude product andthe resulting suspension filtered through Celite to yield a darge orangeproduct. This was then vacuum distilled at 120-145° C./100 mTorr to give7.15 g (73% yield) of a dark orange product.

¹H NMR: (500 MHz, C₆D₆): δ=0.84 (t, 6H), δ=1.1 (d, 18H), δ=1.69 (s, 9H),δ=1.7 (s, 12H), δ=1.96 (q, 4H). δ=4.5 (m, 3H).

Example 14 Synthesis oftitanium(2,4,5-trimethyl-imidazolato)triisopropoxide,

To a solution of 2.00 g (7.68 mmol) TiCl(OPr^(i))₃ in 50 mL of THF at−40° C. was added 1.26 g (7.68 mmol) of 2,4,5-trimethyl-imidazolatelithium salt dissolved in 25 mL THF drop-wise. The reaction was refluxedfor 16 hours after which all volatiles were removed under vacuum. Theresulting orange-red foamy solid was partially dissolved in 100 mL oftoluene and a pale orange solid was filtered off weighing 0.75 g. Thefiltrate was pumped under vacuum to a viscous dark brown oil weighing1.46 g. The crude product can be further purified by vacuumdistillation. The crude yield was 57%.

Example 15 Synthesis oftitanium(2-ethyl-4-methyl-imidazolate)triisopropoxide

To a solution of 1.80 g (6.91 mmol) TiCl(OPr^(i))₃ in 50 mL of THF at−40° C. was added 1.00 g (6.91 mmol) of 2-ethyl-4-methyl-imidazolatelithium salt dissolved in 25 mL THF drop-wise. The reaction was stirredat room temperature for three days after which all volatiles wereremoved under vacuum. The resulting yellow-orange solid was partiallydissolved in warm toluene and filtered. The filtrate was pumped undervacuum to a viscous brown oil. The crude product can be further purifiedby vacuum distillation.

Example 16 Synthesis of di-titaniumbis(2,4-di-tert-butyl-imidazolate)hexaethoxide

To a solution of 1.00 g (4.58 mmol) of TiCl(OEt)₃ in 30 mL of THF at−40° C. was added a suspension of 0.85 g (4.58 mmol)2,5-di-tert-butyl-imidazolate lithium salt in 20 mL of THF drop-wise.The reaction was stirred for 16 hours at room temperature after whichall volatiles were removed under vacuum. The resulting foamy brown solidwas partially dissolved in hexanes and 0.18 g of an off-white solid wasfiltered off. The filtrate was pumped down to 1.64 g of a foamybrown-yellow solid. Purification was accomplished by sublimation. Thecrude yield was 99%.

A sample of crystalline solid was characterized by X-ray single crystalanaylsis. The structure shows a dimer wherein each titanium iscoordinated to a 2,5-di-tert-butylimidazolate anion ring in an eta-1fashion. Both titanium centers are also coordinated to a total of sixethoxide anions, two of which bridge both metal centers, see FIG. 3.TGA/DSC showed a melting point of 77.6° C., involatile residue of <4 wt%, see FIG. 4.

¹H-NMR (500 MHz, C₆D₆) δ (ppm): 4.24 (b, 12H, OCH₂CH₃), 1.67 (s, 18H,imid), 1.65 (s, 18H, imid), 1.04 (b, 18H, OCH₂CH₃).

Example 17 Synthesis of titanium(2-isopropyl-4,5-di-(1,1-dimethylpropyl)imidazolate)triisopropoxide

To a solution of 2.64 g (10.54 mmol) of TiCl(OPr^(i))₃ in 30 mL of THFwas added 2.74 g (10.54 mmol) of2-isopropyl-4,5-di-tert-amyl-imidazolate salt synthesized in situ. Uponaddition, the reaction mixture became a vibrant burgundy red. Thereaction was stirred at room temperature for 16 hours, after whichvolatiles were removed under vacuum. The residual was partiallydissolved in hexanes and 0.46 g of a white solid was filtered off. Thefiltrate was pumped down to a red-brown sticky oil and purified viavacuum distillation to obtained 3.26 g of a dark red-brown oil.

¹H-NMR (500 MHz, C₆D₆) δ (ppm): 4.46 (sept, 3H, OCH(CH₃)₂), 3.47 (sept,1H, imid), 2.07 (q, 4H, imid), 1.69 (s, 12H, imid), 1.62 (d, 6H, imid),1.11 (d, 18H, OCH(CH₃)₂), 1.01 (t, 6H, imid).

Example 18 Synthesis of di-titaniumbis(2,4-di-tert-butylimidazolate)hexaisopropoxide

Under a blanket of dry nitrogen, 0.45 g (2.5 mmoles) of2,4-di-tertbutylimidazole) dissolved in 10 ml of dry tetrahydrofuranwere added, with stirring, to 0.1 g of potassium hydride (2.5 mmoles) in10 ml of THF. After 20 minutes the evolution of hydrogen ceased leavinga clear yellow solution. This was then added over 5 minutes to 0.65 g(2.5 mmoles) of chlorotriisopropoxytitanium dissolved and stirring in 10ml of tetrahydrofuran at room temperature. The resulting mixture wasthen stirred for 1 hour at room temperature after which the solvent wasremoved by the application of vacuum to yield yellow brown solid. Thiswas sublimed at 140° C. to yield 0.8 g (80%) ofbis(2,4-di-tert-butylimidazoly-tri-isopropoxy titanium) as a yellowcrystalline solid X-crystallography confirmed it as a dimeric structurewhere each titanium is coordinated to a 2,5-di-tert-butylimidazolateanion ring in an eta-1 fashion. Both titanium centers are alsocoordinated to a total of six ethoxide anions, two of which bridge bothmetal centers, see FIG. 5. Thermogravimetric analysis/differentialscanning calorimetry (TGA/DSC) showed a melting point of 67.6° C. and aninvolatile residue of <2 wt %, see FIG. 6.

¹H NMR: (500 MHz, C₆D₆): δ=1.26 (d, 36H), δ=1.75 (s, 18H), δ=1.84 (s,18H), δ=4.54 (m, 6H), δ=7.44 (s, 2H).

Example 19 Synthesis of titaniumbis(2,5-di-tert-butylimidazolate)diisopropoxide

To a solution of 12.89 g (49.45 mmol) of TiCl(iPrO)₃ in 200 mL of THFwas added 9.21 g (49.45 mmol) of 2,5-di-tert-butyl imidazolate lithiumsalt. The reaction was stirred at room temperature for 16 hours afterwhich all volatiles were removed under vacuum to a yellow solid. Theresidual was partially dissolved in 200 mL of hexanes and 2.04 g ofsolid was filtered off. The filtrate was stripped of solvent by vacuum,and the crude bis((2,4-di-tert-butylimidazoly)-tri-isopropoxy titanium)thus formed was then disproportionated tobis(2,5-di-tert-butylimidazolate)bis(isopropoxy)titanium and titaniumtetra-isopropoxide by prolonged vacuum distillation at 100 mTorrand >100° C. The titanium tetra-isopropoxide was distilled out as themore volatile fraction leaving the desired product behind. Structureconfirmed by X-ray, which shows a monomeric structure where twoimidazolate anions coordinate eta-1 to titanium which is alsocoordinated to two isopropoxide anions, see FIG. 7.

¹H-NMR (500 MHz, C₆D₆) δ (ppm): 7.12 (s, 2H, imid), 4.47 (sept, 2H,OCH(CH₃)₂), 1.56 (s, 18H, imid), 1.52 (s, 18H, imid), 1.04 (d, 12H,OCH(CH₃)₂).

Example 20 Synthesis oftitanium(2,4,5-tri-tert-butylimidazolate)triisopropoxide

Under a blanket of dry nitrogen, 4.72 (20 mmoles) of2,4,5-tri-tert-butylimidazole) dissolved in 50 ml of dry THF were added,with stirring, to 0.8 g of potassium hydride (20 mmoles) in 50 ml ofTHF. After 20 minutes, the evolution of hydrogen ceased, leaving a clearsolution. This was then added to 5.21 g (20 mmoles) ofchlorotriisopropoxytitanium dissolved in 20 ml of THF at roomtemperature. The resulting mixture was then stirred for overnight atroom temperature, after which the solvent was removed by the applicationof vacuum to yield a yellow orange solid. This was mixed with 100 m ofhexane, filtered to yield a golden oil, which solidified upon standingat 4° C. overnight. This crude product was then vacuum distilled at 100mToo, collecting 6.5 g (71% yield) of pure product at 120-125° C. X-raycrystallography of crystals grown at 4° C. confirmed the structure as amonomer, where the imidazolate anion is coordinated eta-1 to titanium,which is also coordinated to three isopropoxide anions, See FIG. 8.TGS/DSC showed a melting point of 36.3° C. and an involatile residue of<5 wt %, see FIG. 9.

¹H NMR: (500 MHz, C₆D₆): δ=1.1 (d, 18H), δ=1.7 (s, 18H), δ=1.72 (s, 9H),δ=4.5 (m, 3H).

Example 21 Synthesis of titanium(2,4,5-tri-tert-butyl-imidazolate)trichloride

Solution of 3.50 g (14.83 mmol) of 2,4,6-tri-tert-butyl-imidazole in 10ml of toluene was added to 22.3 ml of 1M TiCl₄ in toluene (22.3 mmol) atRT during ˜5 minutes. The solution turned dark and formation of yellowprecipitate was observed. The slurry was agitated for 24 hours and largeamount of solid was formed. The solid was filtered and washed with 20 mlof toluene. 3.6 g of yellow solid, which was likely a salt of2,4,6-tri-tert-butyl-imidazoliumtri-mu-chlorido-bis[trichloridotitanium(IV)] (Ti₂Cl₉ ⁻). Toluene wasdistilled out from the filtrate under vacuum and residue was dried undervacuum at 80° C. to remove traces of unreacted TiCl₄ and2,4,6-tri-tert-butyl-imidazole (very light yellow solid). The residualmaterial was transferred into 25 ml flask and sublimed under 0.2 torr at80-100° C. to obtain 1.54 g of deep red solid (27% yield based on2,4,6-tri-tert-butyl-imidazole).

Thermal gravimetric and differential thermal analyses indicate thematerial is a volatile solid with mp ˜77° C., vapor pressure >1 torr at150° C. and thermal decomposition temperature above 200° C.

¹H-NMR (500 MHz, d₈-toluene) δ (ppm): 1.35 (s, 18H), 1.41 (s, 9H);¹³C-NMR (500 MHz, d₈-toluene) δ (ppm): 29.5 (3C), 31.3 (6C), 36.8 (2C),37.0 (1C), 168.0 (2C), 181 (1C).

Example 22 Crystal structure oftitanium(2,4,5-tri-tert-butyl-imidazolate)trichloride

Crystals of titanium 2,4,5-tri-tert-butyl-imidazolate trichloride weregrown from its solution in octane and characterized by X-ray singlecrystal anaylsis. Unexpectedly, the structure (FIG. 13) shows titanium(IV) coordinated to the 2,4,6-tri-tert-butylimidazolate anion in aneta-5 fashion in addition to three chloride anions.

Ti(1)-C(1)-2.2962(18), Ti(1)-N(2)-2.3114(15), Ti(1)-N(1)-2.3192(15),Ti(1)-C(2)-2.3774(17), Ti(1)-C(3)-2.3882(17). See FIG. 10. Example 23Synthesis of titanium(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)trichloride

Solution of 4.00 g (15.15 mmol) of2-tert-butyl-4,5-di-tert-pentyl-imidazole in 10 ml of toluene was addedto 22.7 ml of 1M TiCl₄ in toluene (22.7 mmol) at RT during ˜5 minutes.The solution turned dark and formation of yellow precipitate wasobserved. The slurry was agitated for 24 hours and large amount of solidwas formed. The solid was filtered and washed with 20 ml of toluene.4.45 g of yellow solid, which was likely a salt of2-tert-butyl-4,5-di-tert-pentyl-imidazoliumtri-mu-chlorido-bis[trichloridotitanium(IV)](Ti₂Cl₉ ⁻). Toluene wasdistilled out from the filtrate under vacuum and residue was dried undervacuum at 95° C. to remove traces of unreacted TiCl₄ and2-tert-butyl-4,5-di-tert-pentyl-imidazole (light yellow liquid). Theresidual material was transferred into 25 ml flask and sublimed under0.2 torr at 80-100° C. to obtain 1.1 g of deep red solid (17% yieldbased on 2-tert-butyl-4,5-di-tert-pentyl-imidazole).

Thermal gravimetric and differential thermal analyses indicate thematerial is a volatile solid with mp ˜59° C. and vapor pressure >1 torrat 150° C. and thermal decomposition temperature above 200° C.

¹H-NMR (500 MHz, d₈-toluene) δ (ppm): 0.54 (t, 6H), 1.44 (s, 9H), 1.45(s, 6H), 1.49 (s, 6H), 1.60 (q, 2H), 1.64 (q, 2H).

Example 24 Crystal structure oftitanium-2-tert-butyl-4,5-di-(11,-dimethylpropyl-imidazolate trichloride

Crystals of titanium 2,4,5-tri-tert-butyl-imidazolate trichloride weregrown from its solution in octane and characterized by X-ray singlecrystal analysis (See FIG. 14). Unexpectedly, the structure showstitanium (IV) coordinated to 2-tert-butyl-4,5-di-tert-pentyl-imidazolateanion in an eta-5 fashion in addition to three chloride anions:Ti(1)-C(1)-2.2939(15), Ti(1)-N(2)-2.3104(13), Ti(1)-N(1)-2.3136(13),Ti(1)-C(2)-2.3880(16), Ti(1)-C(3)-2.4038(15), see FIG. 11.

Example 25 Synthesis of titanium(2,4,5-tri-tert-butyl-imidazolate)dichloride methoxide

Solution of 0.200 g (0.51 mmol) of titanium2,4,5-tri-tert-butyl-imidazolate trichloride in 2 ml of d₈-toluene wasadded to 0.08 g (2.11 mmol) of lithium methoxide at RT in a small vailinside nitrogen purged glove box. The slurry was agitated at RT for 16hours and filtered. Solution analysis by ¹H and ¹³C NMR indicated ˜78%conversion into titanium 2,4,5-tri-tert-butyl-imidazolatedichloridemethoxide:

¹H-NMR (500 MHz, d₈-toluene) δ (ppm): 1.41 (s, 9H), 1.42 (s, 18H); 3.98(s, 3H(OCH₃ group); ¹³C-NMR (500 MHz, d₈-toluene) δ (ppm): 29.5 (3C),31.3 (6C), 36.8 (2C), 37.0 (1C), 74.5 (1C, (OCH₃), 163.2 (2C), 175 (1C).

Example 26 Synthesis of titanium(2,4,5-tri-tert-butyl-imidazolate)chloride dimethoxide

To a Solution of 0.500 g (1.28 mmol) of2,4,5-tri-tert-butyl-imidazolyltitanium trichloride in 7 ml of toluenewas added to 0.235 g (6.2 mmol) of lithium methoxide at RT. The slurrywas agitated at RT for 2 days followed by 16 hours at 50° C. During thetreatment the color of the slurry changed from deep red to yellow.Mixture of lithium methoxide and lithium chloride was filtered off andsolvent was distilled under vacuum at 50° C. Residue analysis by ¹H and¹³C NMR indicated presence of a mixture of2,4,5-tri-tert-butyl-imidazolyltitanium dichloride methoxide (˜13 mol %)and 2,4,5-tri-tert-butylimidazolyltitanium chloride dimethoxide (˜87 mol%):

¹H-NMR (500 MHz, d₈-toluene) δ (ppm): 1.40 (s, 9H), 1.48 (s, 18H); 4.05(s, 6H(OCH₃ group); ¹³C-NMR (500 MHz, d₈-toluene) δ (ppm): 29.7 (3C),31.8 (6C), 36.4 (2C), 36.2 (1C), 69.5 (2C, (OCH₃), 157.0 (2C), 170 (1C).

Example 27 Synthesis of zirconium(2,4,5-tri-tert-butylimidazolate)tri(dimethylamide)

In a N₂-purged glove box a 100 mL, 3-neck RB flask equipped with amagnetic stir bar, gas inlet tube, thermocouple, and reflux condenserwas charged with tetrakis(dimethylamino)zirconium (2.0 g, 7.5 mmol) and20 mL anhydrous toluene. 2,4,5-tri-tert-butyl-imidazole (1.94 g, 8.2mmol) was dissolved in 20 mL of anhydrous toluene and mixed directlywith the zirconium precursor solution at room temperature. Thereactotion flask was moved to a nitrogen-purged Schlenk line. Themixture was refluxed for 16 hours with a purge of 1 mL/min of drynitrogen through the gas inlet tube. The toluene was removed undervacuum and the reaction was further heated between 110° C. and 120° C.for an additional 9 hours with a 1 mL/min nitrogen purge through the gasinlet tube. Volatile products were removed at 100 mTorr and 60° C. Theproduct was transferred to a sublimation unit where unreacted TDMAZ and2,4,5-tri-tert-butylimidazole were removed at bath temperatures rangingfrom 50° C. to 100° C. at 40 mTorr pressure. The cold finger wasreplaced and the product was isolated by further sublimation onto anair-cooled finger at bath temperatures ranging from 120° C. to 140° C.at 30 mTorr pressure 1.7 g (50% isolated yield) of a white,crystalline-solid product. NMR (d₈-toluene): ¹H −1.47 (s, 18H), 1.48 (s,9H), 2.99 (s, 18H); ¹³C{¹H} −30.35 (3C), 302.65 (6C), 35.50 (2C), 36.46(2C), 45.53 (6C, —N(CH₃)₂), 151.16 (2C), 168.53 (1C).

Thermal gravimetric and differential thermal analyses indicate that thematerial is a volatile solid with mp ˜230° C. and vapor pressure >1 torrat 200° C.

Example 28 Synthesis ofcobalt(2,4,5-tri-tert-butylimidazolate)(cyclopentadienide)

Under a blanket of nitrogen, 2.36 g (10 mmoles) of2,4,5-tri-tert-butylimidazole dissolved in 20 ml of THF were added to0.4 g (10 mmoles) of potassium hydride stirring in 80 ml of THF. Whenthe bubbling of released hydrogen ceased, 1.3 g (10 mmoles) of anhydrouscobalt dichloride were added and the resulting mixture stirred overnightat room temperature. 5.0 ml of 2.0M sodium cyclopentadienyl in THF (10mmoles) were then added and the mixture again stirred overnight at roomtemperature. The THF was then removed by vacuum, 100 ml of hexane addedwith mixing and the resulting suspension filtered and the hexane thenremoved by vacuum to yield the crude product as a dark reddish brownpaste. This was then vacuum distilled at 100 mTorr and 2.19 g of productwas collected at 120-140° C. (61% yield), structure confirmed by GCMSshowing the parent ion at 359 mu. Elemental analysis carbon=65.87 wt %(vs 66.85 theoretical), hydrogen=9.19 wt % (vs 8.91 theoretical),nitrogen=7.77 wt % (vs 7.80 theoretical). TGA showed an involatileresidue of <6 wt %, see FIG. 12

Example 29 Synthesis of cobalt(2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazolate)(cyclopentadienide)

Under a blanket of nitrogen, 2.5 g (8.3 mmoles) of potassium2-tert-butyl-4,5-di-tert-amylimidazoyl were dissolved in 50 ml of THFand 1.07 g (8.3 mmoles) of anhydrous cobalt chloride were added andstirred overnight at room temperature. To this mixture, 4.0 ml (8.3mmoles) of 2.0M sodium cyclopentadienyl in THF was added and theresulting mixture stirred overnight at room temperature. The THF wasthen removed by vacuum, 100 ml of hexane added with mixing and theresulting suspension filtered and the hexane then removed by vacuum toyield the crude product as a dark reddish brown paste. This was thenvacuum distilled at 100 mTorr and 2.05 g of product was collected at120-140° C. (64% yield), structure confirmed by GCMS showing the parention at 387 mu. TGS/DSC showed a melting point of 84.6 C and aninvolatile residue of <7 wt %, see FIG. 13.

Example 30 Synthesis of iron(2,4,5-tri-tert-butylimidazoate)(cyclopentadienide)

Under a blanket of nitrogen, 1.18 g (5 mmoles) of2,4,5-tri-tert-butylimidazole in 10 ml of THF were added to 0.2 g (5mmoles) of potassium hydride stirring in 10 ml of THF. After thehydrogen evolution ceased, 0.64 g (5 moles) of anhydrous iron dichloridewere added and the resulting mixture stirred overnight. 2.5 ml of 2.0Mof sodium cyclopentadienyl in THF (5 mmoles) were then added and themixture stirred for 30 minutes. The solvent was then removed undervacuum and the crude product distilled out of the crude product as 0.91g (51% yield) of an orange semisolid paste. This product was thenredistilled under vacuum to yield an orange red oil that crystallized,structure confirmed by X-ray crystallography, which showed the complexto be a monomer with both the 2,4,5-tri-tert-butylimidazolate andpentamethylcyclopentadienide anions to be coordinated eta-5 to the ironcenter, see FIG. 14. TGA/DSC showed a melting point of 39.4° C. with aninvolatile residue <4.0 wt %, see FIG. 15.

Example 31 Synthesis of ruthenium(2,4,5-trimethylimidazolate)(pentamethylcyclopentadienide)

To a solution of 0.20 g (0.74 mmol)chloro(pentamethylcyclopentadienyl)ruthenium(II) tetramer in 3 mL THF atroom temperature was added 0.09 g (0.74 mmol) 2,4,5-trimethylimidazolatelithium salt dissolved in 2 mL of THF drop-wise. Reaction mixture wasstirred for several weeks after which volatiles were removed undervacuum. Isolated a brown solid that was loaded into a sublimer andheated to 125° C. under 150 mTorr vacuum. A total of 0.18 g of a yellowcrystalline solid was collected from the sublimer cold finger and walls.The yield was 69%.

A sample of crystalline solid was characterized by X-ray single crystalanaylsis. The structure shows a monomeric ruthenium complex, where themetal center is coordinated to both the 2,4,5-trimethylimidazolyl ringand the pentamethylcyclopentadienyl ring in i fashion, see FIG. 16.TGA/DSC showed a melting point of 130.6° C. and an involatile residue of<2 wt %, see FIG. 17.

¹H-NMR (500 MHz, C₆D₆) δ (ppm): 2.36 (s, 3H), 1.93 (s, 6H), 1.66 (s,15H).

Example 32 Synthesis of ruthenium(2-ethyl-4-methylimidazolate)(pentamethylcyclopentadienide)

To a solution of 0.25 g (0.92 mmol)chloro(pentamethylcyclopentadienyl)ruthenium(II) tetramer in 7 mL THF atroom temperature was added 0.11 g (0.92 mmol)2-ethyl-4-methylimidazolate lithium salt directly. Reaction mixture wasstirred for 16 hours, after which volatiles were removed under vacuum.Isolated a burgundy foam that was extracted with hexanes and filtered.Filtrate was pumped under vacuum to 0.22 g of an oil that quicklysolidified. Loaded solid into a sublimer and heated to 125° C. under 150mTorr vacuum. A yellow crystalline solid was collected from the sublimercold finger. The yield was 69%, based off of crude.

¹H-NMR (500 MHz, C₆D₆) δ (ppm): 5.42 (s, 1H), 2.75 (q, 2H), 1.92 (s,3H), 1.70 (s, 15H), 1.39 (t, 3H).

TGA/DSC showed a melting point of 64.1° C. and an involatile residue of<1.0 wt %, see FIG. 18.

Example 33 Synthesis of ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(pentamethylcyclopentadienide)

To a solution of 0.25 g (0.92 mmol)chloro(pentamethylcyclopentadienyl)ruthenium(II) tetramer in 7 mL THF atroom temperature was added 0.16 g (0.92 mmol)2-tert-butyl-4-methyl-5-ethylimidazolate lithium salt directly. Reactionmixture was stirred for 16 hours, after which volatiles were removedunder vacuum. Isolated a dark brown waxy solid that was extracted withhexanes and filtered. Filtrate was pumped under vacuum to 0.27 g of abrown solid. Loaded solid into a sublimer and heated to 85° C. under 150mTorr vacuum. A yellow crystalline solid was collected from the sublimercold finger. The yield was 73% based off of crude.

A sample of crystalline solid was characterized by X-ray single crystalanaylsis. The structure shows a monomeric ruthenium complex with themetal center coordinated to both the2-tert-butyl-4-methyl-5-methylimidazolate andpentamethylcyclopentadienide anions ring and thepentamethylcyclopentadienyl ring in an eta-5 fashion, see FIG. 19.TGA/DSC showed a melting point of 73.8° C. and an involatile residue of<1.0 wt %, see FIG. 20.

¹H-NMR (500 MHz, C₆D₆) δ (ppm): 2.23 (q, 2H), 1.88 (s, 3H), 1.65 (s,15H), 1.50 (s, 9H), 1.12 (t, 3H).

Example 34 Synthesis of ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(pentamethylcyclopentadienide)

1.1 g (37 mmoles) ofpotassium(2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazolate) dissolvedin 25 ml of THF were added to 1 g (0.0037 moles) of ruthenium(pentamethylcyclopentadienide) chloride dissolved in 75 ml of dry THFand the resulting mixture stirred overnight at room temperature. Thesolvent was then removed by vacuum, 100 ml of dry hexane then added andthe resulting mixture thoroughly stirred then filtered. The hexane wasthen removed by vacuum to yield 1.13 g of crude ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate).(pentamethylcyclopentadienide). Structure confirmed by GCMS, parent iondetected at 499 mu. The structure was also confirmed by X-ray structuralanalysis of a sample of crude material which was sublimed thenrecrystallized from hexane. This shows the imidazolate andcyclopentadienide anions to both be coordinated eta-5 to ruthenium, seeFIG. 21.

Example 35 Synthesis ofruthenium(pentamethylcyclopentadienide)(imidazolate)

To a suspension of 0.50 g (1.84 mmol) of ruthenium(II)(pentamethylcyclopentadienide) chloride tetramer in a mixture of 16 mLof THF and hexanes was added 0.21 g (1.84 mmol) lithium imidazolate. Thereaction mixture turned a deep purple and was refluxed for 16 hoursafter which all volatiles were removed under vacuum. The residual solidwas partially dissolved in warm hexanes and 0.25 g of a dark purplesolid was filtered off. Solvent was removed from the hexane by vacuum toyield a purple foam-like solid weighing 0.13 g. Analysis of the filtrateby ¹H-NMR showed many impurities. TGA of the insoluble solid showed aresidual mass of 75%.

Example 36 Synthesis ofmanganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate)Itricarbonyl

Inside a nitrogen-purged glove box a 14/20 3-neck, 100 mL round bottomflask with a magnetic PTFE stir bar was charged with the 4.81 g (17.5mmol) of 2-tert-butyl-4,5-di-tert-pentyl-imidazole and 50 ml of hexanes.The flask was fitted with a vacuum takeoff, pressure-equalizing dropfunnel, and a rubber septum. The setup was moved to a nitrogen-purgedSchlenk manifold where the contents were cooled to −40° C. in a coldacetone bath. 11.9 ml of 1.6 M solution of n-butyllithium in hexane(19.0 mmol) were added drop-wise via syringe over 15 minutes with rapidstirring wherein no temperature changes or exothermic activity wereobserved. The resulting solution was stirred at low temperature for onehour, then allowed to warm to room temperature by removing the coldbath. Upon standing for an additional hour, the solution remainedcolorless, but became very thick with a consistency similar to honey.The solution was cooled to 0° C. and treated drop-wise over 30 minuteswith the solution of 5.00 g (18.2 mmol) of manganese pentacarbonylbromide dissolved in 30 ml of anhydrous THF, and loaded to the dropfunnel. The resulting mixture was allowed to warm to room temperatureand stir for 16 hours. Under a nitrogen purge, the drop funnel wasreplaced with a ground-glass plug and the septum with a short-pathdistillation column. At a pressure of ˜200 torr, the majority of thesolvent was distilled into a receiver using a bath temperature of ˜50°C. The receiver was exchanged with a clean, dry udder and the remainingsolvent was removed under full vacuum. The distillation was continuedunder full vacuum (˜50 mTorr) where at a bath temperature of 80-100° C.unreacted yellow-crystalline BrMn(CO)₅ was removed by sublimation.Distillation column was exchanged with a short path condenser and thevacuum takeoff was replaced with a glass plug. The bath was heated to125° C. where over 2-3 hours an orange-red crystalline solid wasdistilled out and crystallized on the cold parts of condenser andreceiver. 3.07 g (47 isolated yield) of manganese2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate tricarbonyl wascollected. IR (v (CO))=1960 and 2030 cm⁻¹. ¹H NMR (d₈-toluene): 0.66 (t,6H), 1.33 (s, 6H), 1.35 (s, 9H), 1.41 (m, 2H), 1.44 (s, 6H), 1.59 (m,2H); ¹³C NMR (d₈-toluene): 9.28 (2C), 28.29 (2C), 29.66 (3C), 31.22(2C), 32.74 (1C), 36.54 (2C), 36. 81 (2C), 132.64 (2C), 144.01 (1C),224.3 (3C(CO)). TGA (conditions 90 ccm of N₂ and 10° C./min heatingrate) showed an involatile residue of <0.5 wt % and an estimated vaporpressure above 1 torr at 150° C., see FIG. 22.

Example 37 Differential scanning calorimetry ofmanganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate)ltricarbonyl

In a sealed pressure capsule at 10 C/min heating rate indicated an onseton endothermal decomposition around 250° C. Lower onset of thermaldecompositionmanganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate)tricarbonylcompare to prior art manganese tricarbonyl complex manganese(methycyclopentadieide0 tricarbonyl, onset of decomposition >300° C.)suggests higher reactivity of manganese imidazolate complexes of thisinvention in chemical vapor deposition reactions. FIG. 23 shows the.thermal gravimetric analysis ofmanganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate)Itricarbonyl (solid) and manganese(methylcyclopentadienide)tricarbonyl(dashed).

Example 38 Reactivity ofmanganese(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate)tricarbonyltoward hydrogen

10 ml SS vessel was charged with 2.1 g of manganese2-tert-butyl-4,5-di-tert-pentyl-imidazolate tricarbonyl and 121 psi ofhydrogen. The vessel was heated to 250° C. at 2° C./min heating ratefollowed by 12 hour isothermal heating at 250° C. Pressure increase dueto release of gas was observed during isothermal heating at 250° C.After cooling the reaction vessel to RT residual sample pressure wasmuch higher than initial sample pressure (250 psig) indicating releaseof carbon monoxide from the sample at 250° C. GC analysis of the gasesevolved during the experiment also indicated presence of carbonmonoxide. No reaction between the prior art manganese tricarbonylcomplex (manganese methycyclopentadienide tricarbonyl) and hydrogen wasobserved under identical condition as unchangedmethylcyclopentadienylmanganese tricarbonyl was recovered after heatingunder 145 psi of hydrogen for 16 hours at 250° C.

Example 39 Synthesis of lanthanum(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate)diiodidebis(tetrahydrofuran)

Lanthanum (III) iodide (1.0 g, 0.002 mol) was stirred in 50 mL of THFfor 30 mins at room temperature. Potassium2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate (0.6 g, 0.002 mol)was added, and the resulting mixture was refluxed for 60 hours. THF wasremoved by vacuum, followed by hexane extraction, then filtration. Thehexane was removed by vacuum, and the resulting solid was crystallizedto isolate the final product.

Yield=1.18 g, 26.3%

NMR: 4.25 (4H, s), 1.70 (4H, q), 1.633 (21H, s), 1.415 (4H, m), 0.725(6H, t).

Structural determination by X-ray analysis showed a monomeric lanthanumcomplex where the metal center is coordinated to the2-tert-butyl-4,5-di-(11-dimethylpropyl)imidazolate anion in an eta-5fashion along with two iodide anions and two molecules oftetrahydrofuran, see FIG. 24.

Example 40 Synthesis of Cerium2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazolate diiodidebis(tetrahydrofuran)

Cerium (III) iodide (2.0 g, 0.0038 mol) was stirred in 50 mL of dry THFfor 30 mins at room temperature. Potassium2-tert-butyl-4,5-di(1,1-dimethylpropyl)imidazolate (1.15 g, 0.0038 mol)was added, and the resulting mixture was refluxed for 90 hours. Thesolvent was removed by vacuum, followed by hexane extraction of theresulting solid. The hexane was removed by vacuum to yield the finalproduct.

Yield=1.18 g, 47%. X-ray crystallography of the final productrecrystallized from hexane showed it to be a monomer with the cerium ioncoordinated to the imidazolate in an eta-5 mode in addition to twoiodide ions and two molecules of THF, see FIG. 25

Example 41 Synthesis of Europium2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate iodidebis(tetrahydrofuran)

Europium II iodide (1.0 g, 0.0025 mol) was stirred in 50 mL of THF for30 mins at room temperature. Potassium2-t-butyl-4,5-di-(1,1-dimethylpropyl)-imidazolate (1.51 g, 0.0050 mol)was added, and the resulting mixture was refluxed for 41 hours. THF wasremoved by vacuum, followed by hexane extraction, then filtration. Thehexane was removed by vacuum to yield 1.32 g of solid crude product.Sublimation of a sample of this crude product followed by adding excesstetrahydrofuran, evaporating the solvent and then recrystallizing theresulting residue from hexane yielded crystals for X-ray analysis whichconfirmed the product to be a 1-D polymeric structure where theimidazolates bind eta-5 to the europium ions which are in turn bridgedby iodide ions, see FIG. 26.

Example 42 Synthesis of di-Europiumtetra-(2-tert-butyl-4,5-di-(1,1-dimethylpropyl)imidazolate

Europium II iodide (1.0 g, 0.0025 mol) was stirred in 50 mL of THF for30 mins at room temperature. Potassium 2,4,5-tri-tert-tbutylimidazolate(1.37 g, 0.0050 mol) was added, and the resulting mixture was refluxedfor 60 hours. THF was then removed by vacuum, followed by hexaneextraction, then filtration and solvent removal by vacuum. This yielded0.985 g (79%) of crude product. A sample of this product was thensublimed at 150 C under vacuum to yield a yellow orange solid which wasthen crystallized in hexane. X ray analysis confirmed the structure ofthe product as a dimer containing two europium ions and four imidazolateanions. Two imidazolate anions are coordinated to europium in an eta-5fashion and two imidazolate anions are bridging the metal ions, see FIG.27.

1. A ruthenium compound represented by Structure A:

wherein R¹ can be same or different selected from group consisting oflinear or branched C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl;R²⁻³ are same or different selected from group consisting of hydrogen,methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,tert-butyl, isomers of pentyl; When R² is hydrogen, R¹ and R³ can not beboth C1 alkyl; R⁴⁻⁸ can be same or different selected from groupconsisting of hydrogen, linear or branched C₁₋₁₀ alkyls, C₁₋₁₀alkoxyalkyl, C₁₋₁₀ aminoalkyl.
 2. The ruthenium compound of claim 1wherein R¹ is selected from the group consisting of methyl, ethyl,n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, tert-amyl; R² isselected from the group consisting of ethyl, n-propyl, i-propyl,n-butyl, sec-butyl, tert-butyl, tert-amyl.
 3. The ruthenium compound ofclaim 1 wherein R⁴ is selected from the group consisting of methyl,ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, tert-amyl;R⁵⁻⁸ are hydrogen.
 4. The ruthenium compound of claim 1 selected fromthe group consisting of ruthenium(2,4,5-trimethylimidazolate)(pentamethylcyclopentadienide); ruthenium(2,4,5-trimethylimidazolate)(ethylcyclopentadienide);ruthenium(2,4,5-trimethylimidazolate)(n-propylcyclopentadienide);ruthenium (2,4,5-trimethylimidazolate)(i-propylcyclopentadienide);ruthenium (2,4,5-trimethylimidazolate)(n-butylcyclopentadienide);ruthenium (2,4,5-trimethylimidazolate)(sec-butylcyclopentadienide);ruthenium (2,4,5-trimethylimidazolate)(tert-butylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(pentamethylcyclopentadienide);ruthenium (2-ethyl-4-methylimidazolate)(methylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(ethylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(n-propylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(i-propylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(n-butylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(sec-butylcyclopentadienide);ruthenium(2-ethyl-4-methylimidazolate)(tert-butylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(pentamethylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(methylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(ethylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(n-propylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(i-propylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(n-butylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(sec-butylcyclopentadienide);ruthenium(2-tert-butyl-4-methyl-5-ethylimidazoate)I(tert-butylcyclopentadienide);ruthenium (2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(pentamethylcyclopentadienide); ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(methylcyclopentadienide);ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(ethylcyclopentadienide);ruthenium (2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(n-propylcyclopentadienide);ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(1-propylcyclopentadienide);ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(n-butylcyclopentadienide);ruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(sec-butylcyclopentadienide);andruthenium(2-tert-butyl-di(1,1-dimethylpropyl)imidazolate)(tert-butylcyclopentadienide.5. A ruthenium compound of the formula represented by Structure B:

wherein R¹ is selected from group consisting of linear or branched C₁₋₁₀alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl; R²⁻³ can be same ordifferent selected from group consisting of hydrogen, linear or branchedC₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl, C₁₋₁₀ aminoalkyl; (L) is a neutralcoordinating ligand selected from ether, polyether, furans, amine,polyamine or alkoxyamine, pyridine, N-methylimidazole, olefin, diolefin,triolefin or polyolefin, alkyne, silylolefin, silyalkyne carbonmonoxide, nitrile, isonitrile, silylnitrile or isocyanide, alkylphosphine, and aromatic phospine; (v) is 0-4; (X) is a mono anionselected from the group consisting of C₁₋₁₀ alkyls, C₁₋₁₀ alkoxyalkyl,C₁₋₁₀ aminoalkyl, halides; alkoxy, hydride, amide, beta-diketonates,acetates, ketoiminates, diimines, alkoxides, amides, beta-ketoesters,amidinates, guanidinates, cyclopentadienyl, cyanide, isocyanide,pyrrolyl, formate, acetate, cyanate, oxalate, malonate, phenoxide,thiolate, trialkylsiloxide, bis(trialkylsilyl)amide, sulfide, nitrate,alkyl, silylalkyl, fluoroalkyl, aryl, hydride, pyrrolyl, and halide;m=0, 1; (w)=2, 3; p=1,
 2. 6. The ruthenium compound of claim 5 whereinR¹ is selected from the group consisting of methyl, ethyl, n-propyl,i-propyl, n-butyl, sec-butyl, tert-butyl, tert-amyl; R² and R³ areselected from the group consisting of hydrogen, methyl, ethyl, n-propyl,i-propyl, n-butyl, sec-butyl, tert-butyl, tert-amyl.
 7. The rutheniumcompound of claim 5 wherein R¹⁻³ are selected from the group consistingof i-propyl, tert-butyl, tert-amyl; m=v=0; w=p=2.
 8. The rutheniumcompound of claim 5 wherein R¹⁻³ are selected from the group consistingof i-propyl, tert-butyl, tert-amyl; m=0; L is selected from the groupconsisting of Cl, Br, I; w=2, p=1.
 9. The ruthenium compound of claim 5wherein R¹⁻³ are selected from the group consisting of i-propyl,tert-butyl, tert-amyl; m=0; L is selected from the group consisting ofmethyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl,tert-amyl; w=2, p=1.
 10. A process where a metal compound of claim 1 isused as a volatile precursor for the deposition of metal containing thinfilms by a process selected from the group consisting of ALD, CVD,PECVD, pulsed CVD and molecular layer deposition; over a temperaturerange of 0° C. to 1000° C. and a pressure of 0.1 Torr to 1 atmosphere.11. A process where a metal compound of claim 5 is used as a volatileprecursor for the deposition of metal containing thin films by a processselected from the group consisting of ALD, CVD, PECVD, pulsed CVD andmolecular layer deposition; over a temperature range of 0° C. to 1000°C. and a pressure of 0.1 Torr to 1 atmosphere.
 12. A process using themetal compounds of claim 1 are used to grow thin metal containing filmsby spinning a solution of them onto a substrate and then reacting theresulting layer of precursor to give the desired metal containing film.13. A process using the metal compounds of claim 5 are used to grow thinmetal containing films by spinning a solution of them onto a substrateand then reacting the resulting layer of precursor to give the desiredmetal containing film.
 14. A process where a metal compound of claim 1is used as volatile precursors for the growth of phase change alloys bythe processes selected from the group consisting of ALD, CVD, PECVD,pulsed CVD, and Molecular layer Deposition.
 15. A process where a metalcompound of claim 5 is used as volatile precursors for the growth ofphase change alloys by the processes selected from the group consistingof ALD, CVD, PECVD, pulsed CVD, and Molecular layer Deposition.
 16. Theprocess of claim 10 wherein these thin films are grown by depositionfrom a solution of these precursors in a super critical fluid.
 17. Theprocess of claim 11 wherein these thin films are grown by depositionfrom a solution of these precursors in a super critical fluid.
 18. Theprocess of claim 16 wherein the super critical fluid is carbon dioxide.19. The process of claim 17 wherein the super critical fluid is carbondioxide.
 20. A process using a metal compound of claim 1 wherein theprocess is selected from the group consisting of ALD, CVD, pulsed CVD,PECVD, and molecular layer deposition; using a reactor pressure between0.001-1000 Torr; a temperature from 0-1000° C.; reacting the metalcompound with an oxidant selected from the group consisting of water,alcohol, oxygen, ozone, nitrous oxide, nitrogen dioxide, hydrogenperoxide and combinations thereof, to grow a metal oxide containingfilm.
 21. A process using a metal compound of claim 10 wherein theprocess is selected from the group consisting of ALD, CVD, pulsed CVD,PECVD, molecular layer deposition; using a reactor pressure between0.001-1000 Torr; a temperature from 0-1000° C.; reacting with an oxidantselected from the group consisting of water, alcohol, oxygen, ozone,nitrous oxide, nitrogen dioxide, hydrogen peroxide and combinationsthereof, to grow a metal oxide containing film.
 22. A process using ametal compound of claim 1, wherein the process is selected from thegroup consisting of ALD, CVD, pulsed CVD, PECVD, and molecular layerdeposition; using a reactor pressure between 0.001-1000 Torr; atemperature from 0-1000° C.; by reacting the metal compound with areagent of nitrogen source molecules selected from the group consistingof ammonia, amines and mixtures thereof.
 23. A process using a metalcompound of claim 5, wherein the process is selected from the groupconsisting of ALD, CVD, pulsed CVD, PECVD, molecular layer deposition;using a reactor pressure between 0.001-1000 Torr; a temperature from0-1000° C.; by reacting the metal compound with a reagent of nitrogensource molecules selected from the group consisting of ammonia, aminesand mixtures thereof.
 24. A process using a metal compound of claim 1,wherein the process is selected from the group consisting of ALD, CVD,pulsed CVD, PECVD, and molecular layer deposition; using a reactorpressure between 0.001-1000 Torr; a temperature from 0-1000° C.; byreacting the metal compound with a reducing agent selected from thegroup consisting of hydrogen, ammonia, formic acid, hydrazine, alkylhydrazine, silane, alkyl silane, disilane, alkyldisilane, trisilane,alkyl trisilane, borane, alkylborane, alane, alkyl alane.
 25. A processusing a metal compound of claim 5, wherein the process is selected fromthe group consisting of ALD, CVD, pulsed CVD, PECVD, molecular layerdeposition; using a reactor pressure between 0.001-1000 Torr; atemperature from 0-1000° C.; by reacting the metal compound with areducing agent selected from the group consisting of hydrogen, ammonia,formic acid, hydrazine, silane, alkylsilane, alkyl, alkyldisilane,trisilane, alkyltrisilane, borane, alkylborane, alane, alkyl alane. 26.A method of synthesizing the metal compound of claim 1 by directmetallization of the imidazole ligands using a metal reagent selectedfrom the group consisting of n-butyl lithium, n-hexyl lithium, sec-butyllithium, tert-butyl lithium, lithium diisopropylamide, potassiumhydride, sodium hydride, sodium metal, potassium metal, sodiumt-butoxide, and potassium t-butoxide; and then reacting the resultingproduct with a compound selected from the group consisting of metaliodide, metal acetate, metal carboxylate, metal carbonate, metalformate, metal bromide, metal trifluoroacetate, metalhexafluoroacetylacetone, metal trifluoroacetylacetonate, metalacetyacetonate, metal diimine, metal ketoimine, metal amidinate, metalguanidinate and mixtures thereof.
 27. A method of synthesizing thecompounds of claim 5 by direct metallization of the imidazole ligandsusing a metal reagent selected from the group consisting of n-butyllithium, n-hexyl lithium, sec-butyl lithium, tert-butyl lithium, lithiumdiisopropylamide, potassium hydride, sodium hydride, sodium metal,potassium metal, sodium t-butoxide, and potassium t-butoxide; and thenreacting the resulting product with a compound selected from the groupconsisting of metal iodide, metal acetate, metal carboxylate, metalcarbonate, metal formate, metal bromide, metal trifluoroacetate, metalhexafluoroacetylacetone, metal trifluoroacetylacetonate, metalacetyacetonate, metal diimine, metal ketoimine, metal amidinate, metalguanidinate and mixtures thereof.
 28. A method of directly synthesizingcompounds of claim 1 by reacting a an alkylated imidazole using acompound selected from the group consisting of metal amide, metalphenoxide, metal hydroxide, metal alkyl, metal aryl and mixturesthereof.
 29. A method of directly synthesizing a metal compound of claim5 by reacting a polylalkylated imidazole using a compound selected fromthe group consisting of metal amide, metal phenoxide, metal hydroxide,metal alkyl, metal aryl and mixtures thereof.
 30. A method ofsynthesizing the metal compound of claim 1 by reaction of the imidazoleligand with metal in the presence of ammonia.
 31. A process ofdissolving a metal compound of claim 1 in a suitable solvent, andinjecting a resulting solution into a direct liquid injection system forflash vaporization of the precursor and solvent and delivering aresulting vapor stream into a reactor for the growth of metal containingfilms by a process selected from the group consisting of; ALD, CVD,pulsed CVD, PECVD and Molecular Layer Deposition.
 32. A process ofdissolving a metal compound of claim 5 in a suitable solvent, andinjecting a resulting solution into a direct liquid injection system forflash vaporization of the precursor and solvent and delivering aresulting vapor stream into a reactor for the growth of metal containingfilms by a process selected from the group consisting of; ALD, CVD,pulsed CVD, PECVD and Molecular Layer Deposition.